Quantification of TCE Co‐Oxidation in Groundwater Using a 14C–Assay

Bacteria that degrade natural organic matter in groundwater contain oxygenase enzymes that can co‐oxidize trichloroethene (TCE). This degradation pathway is promising for large dilute plumes, but its evaluation is limited because the density of the bacteria with oxygenase enzymes has not been correlated to field scale rates of degradation. A ¹⁴C–TCE assay was developed to determine pseudo first‐order rate constants for the aerobic co‐oxidation of TCE in groundwater. The assay involved incubating ¹⁴C–TCE in samples of groundwater contained in 160 mL serum bottles, and monitoring the accumulation of radiolabel in degradation products. A first‐order rate constant for co‐oxidation was extracted from the rate of accumulation of ¹⁴C in products, accounting for volumetric changes in the serum bottles due to sampling and subsequent changes to the distribution of TCE between the aqueous and gaseous phases. Of the groundwater samples evaluated from 19 wells at five sites, eight samples at three sites had ¹⁴C product accumulation rates that exceeded the accumulation rate in filter‐sterilized groundwater controls. First‐order rate constants ranged from 2.65 to 0.0066 year^?1, which is equivalent to half‐lives of 0.26 to 105 years. Groundwater samples from a few of the wells in which co‐oxidation occurred had volatile organic contaminants in addition to TCE; their presence may have induced the oxygenase enzymes that are needed for TCE co‐oxidation. ¹⁴CO₂ represented ~37% to 97% of the ¹⁴C products that accumulated; the balance of the products was soluble and non‐volatile.     

Examining the Extraction Efficiency of Petroleum-Derived Dissolved Organic Matter in Contaminated Groundwater Plumes

The extraction efficiency of petroleum-derived dissolved organic matter (DOM) was examined for groundwater samples from an aquifer contaminated with crude oil. Five different types of extraction techniques were investigated to determine which method is best suited for the analysis of potentially toxic petroleum-derived DOM. The five types were a liquid-liquid extraction (LLE) with dichloromethane (DCM) and total petroleum hydrocarbons-diesel range (TPH_d) with DCM (EPA method 3510C), and three solid-phase extraction (SPE) stationary phases that are routinely used for extraction of polar analytes from water. For the LLE and TPH_d, that is selective for nonpolar compounds, the extraction efficiency of petroleum-derived DOM decreased downgradient as the petroleum-derived DOM becomes increasingly polar due to biodegradation. In contrast, the average extraction efficiency by the SPE methods was greater than 65% across the gradient. The results showed that SPE is more efficient for extracting petroleum-derived DOM at hydrocarbon-contaminated sites. The use of a method with greater extraction efficiency for partially oxidized hydrocarbons may prove useful in determining relationships between their composition and structure and potential for risks to human health or the environment.     

Soil formation and weathering in a permafrost environment of the Swiss Alps: a multi‐parameter and non‐steady‐state approach

Spatially discontinuous permafrost conditions frequently occur in the European Alps. How soils under such conditions have evolved and how they may react to climate warming is largely unknown. This study focuses on the comparison of nearby soils that are characterised by the presence or absence of permafrost (active‐layer thickness: 2–3 m) in the alpine (tundra) and subalpine (forest) range of the Eastern Swiss Alps using a multi‐method (geochemical and mineralogical) approach. Moreover, a new non‐steady‐state concept was applied to determine rates of chemical weathering, soil erosion, soil formation, soil denudation, and soil production. Long‐term chemical weathering rates, soil formation and erosion rates were assessed by using immobile elements, fine‐earth stocks and meteoric ¹⁰Be. In addition, the weathering index (K + Ca)/Ti, the amount of Fe‐ and Al‐oxyhydroxides and clay minerals characteristics were considered. All methods indicated that the differences between permafrost‐affected and non‐permafrost‐affected soils were small. Furthermore, the soils did not uniformly differ in their weathering behaviour. A tendency towards less intense weathering in soils that were affected by permafrost was noted: at most sites, weathering rates, the proportion of oxyhydroxides and the weathering stage of clay minerals were lower in permafrost soils. In part, erosion rates were higher at the permafrost sites and accounted for 79–97% of the denudation rates. In general, soil formation rates (8.8–86.7 t/km²/yr) were in the expected range for Alpine soils. Independent of permafrost conditions, it seems that the local microenvironment (particularly vegetation and subsequently soil organic matter) has strongly influenced denudation rates. As the climate has varied since the beginning of soil evolution, the conditions for soil formation and weathering were not stable over time. Soil evolution in high Alpine settings is complex owing to, among others, spatio‐temporal variations of permafrost conditions and thus climate. This makes predictions of future behaviour very difficult. Copyright © 2016 John Wiley & Sons, Ltd.     

Efficacy of an In‐Well Sonde to Determine Magnetic Susceptibility of Aquifer Sediment

Magnetite is a natural component of many aquifers. Abiotic degradation of chlorinated solvents by magnetite can be an important mechanism for natural attenuation of these contaminants. The quantity of magnetite in aquifer materials can be estimated by measuring the magnetic susceptibility of the materials. This is most commonly done by determining the magnetic susceptibility of core samples in an analytical laboratory using a magnetic susceptibility meter. Unfortunately, the cost of acquiring core samples often makes an evaluation of abiotic degradation by magnetite economically unrealistic. Downhole sondes (probes) are available for the determination of magnetic susceptibility. In this study, a downhole sonde was evaluated as an affordable alternative to acquiring and analyzing core samples. The sonde was introduced into 10 monitoring wells. The data from the sonde were then compared to data from core samples that were collected from the same elevation as the sonde data. The core samples analyzed in the laboratory were used as the standard against which the sonde data were compared. The downhole sonde reported values that were similar to values reported on core samples. At most wells, the means of the two measurements could not be distinguished at the 95% confidence interval. When the means could be distinguished, they still agreed within a factor of two.     

Preliminary health risk assessment for polybrominated diphenyl ethers and polybrominated dibenzo-p-dioxins/furans in seafood from Guangzhou and Zhoushan, China

Dietary intake is one of the important routes of human exposure to brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs). The use of PBDEs may also result in exposure to polybrominated dibenzo-p-dioxins and dibenzofurans (PBDDs/DFs), as these compounds are impurities in technical mixtures of BFRs and can also be formed unintentionally by the same processes that generate chlorinated dioxins. This study determined the concentrations of polybrominated compounds in common seafood in Guangzhou and Zhoushan, and assessed the health risks of these chemicals via consumption of contaminated seafood. Seafood samples (fish, bivalves, shrimp, crab, and cephalopods) purchased from local markets in 2003 and 2004 were analyzed for PBDEs and PBDDs/DFs. The highest concentration of total PBDEs (46.3 ng g⁻¹ lipid wt.) was detected in fish from Guangzhou, in which BDEs 47 and 209 were the two predominant congeners. The total daily intakes of PBDEs, PBDDs, and PBDFs were, 946, 6.39, and 6.54 pg kg⁻¹ body weight (bw) in Guangzhou, and 489, 4.99, and 7.65 pg kg⁻¹ bw in Zhoushan, respectively. The hazard ratios for PBDDs and PBDFs were both greater than unity, indicating that these compounds may pose some health risks to the local population.     

Integrated monitoring of the hydro-morphodynamics of a beach protected by low crested detached breakwaters

The aim of this paper is to propose an integrated low cost system for monitoring the performance of beach defence works during storms. For this purpose, the site of Igea Marina, Northern Adriatic Sea, Italy, which is protected by low crested detached breakwaters, is selected. The monitoring system is composed by a video installation, for the identification of the shoreline position and of the intertidal bathymetry at high space and time resolution, and a 2DH numerical model, to reconstruct the hydrodynamics induced by coastal defenses. The accuracy of the monitoring system is verified against available measurements of waves and currents performed during a field campaign with acoustic Doppler profilers. Assimilation of data on the shoreline position in 2DH model operatively working is challenging in the improvement of the production of risk maps. These show the current intensities and flooded areas during forecasted storms. First promising results suggest the possibility of setting up an early warning tool.     

Using nitrate to quantify quick flow in a karst aquifer

In karst aquifers, contaminated recharge can degrade spring water quality, but quantifying the rapid recharge (quick flow) component of spring flow is challenging because of its temporal variability. Here, we investigate the use of nitrate in a two-endmember mixing model to quantify quick flow in Barton Springs, Austin, Texas. Historical nitrate data from recharging creeks and Barton Springs were evaluated to determine a representative nitrate concentration for the aquifer water endmember (1.5 mg/L) and the quick flow endmember (0.17 mg/L for nonstormflow conditions and 0.25 mg/L for stormflow conditions). Under nonstormflow conditions for 1990 to 2005, model results indicated that quick flow contributed from 0% to 55% of spring flow. The nitrate-based two-endmember model was applied to the response of Barton Springs to a storm and results compared to those produced using the same model with δ¹⁸O and specific conductance (SC) as tracers. Additionally, the mixing model was modified to allow endmember quick flow values to vary over time. Of the three tracers, nitrate appears to be the most advantageous because it is conservative and because the difference between the concentrations in the two endmembers is large relative to their variance. The δ¹⁸O-based model was very sensitive to variability within the quick flow endmember, and SC was not conservative over the timescale of the storm response. We conclude that a nitrate-based two-endmember mixing model might provide a useful approach for quantifying the temporally variable quick flow component of spring flow in some karst systems.     

A model study of tide- and wind-induced mixing in the Columbia River Estuary and plume

A numerical simulation of circulation in the Columbia River estuary and plume during the summer of 2004 is used to explore the mixing involved as river water is transformed into shelf water. The model is forced with realistic river flow, tides, wind stress, surface heat flux, and ocean boundary conditions. Simulated currents and water properties on the shelf near the mouth are compared with records from three moorings (all in 72 m of water) and five CTD sections. The model is found to have reasonable skill; statistically significant correlations between observed and modeled surface currents, temperature, and salinity are all 0.42–0.72 for the mooring records. Equations for the tidally averaged, volume-integrated mechanical energy budget (kinetic and potential) are derived, with attention to the effects of: (i) Reynolds averaging, (ii) a time varying volume due to the free surface, and (iii) dissipation very close to the bottom. It is found that convergence of tidal pressure work is the most important forcing term in the estuary. In the far field plume (which has a volume 15 times greater than that of the estuary), the net forcing is weaker than that in the estuary, and may be due to either tidal currents or wind stress depending on the time period considered. These forcings lead to irreversible mixing of the stratification (buoyancy flux) that turns river water into shelf water. This occurs in both the plume and estuary, but appears to be more efficient (17% vs. 5%), and somewhat greater (4.2 MW vs. 3.3 MW), in plume vs. estuary. This demonstrates the importance of both wind and tidal forcing to watermass transformation, and the need to consider the estuary and plume as part of a single system.