Effect of lipids on sorption/desorption hysteresis in natural organic matter

The chemical composition and physical conformation of natural organic matter (NOM) play a major role in regulating its capacity to retain hydrophobic organic compounds. Naphthalene and phenanthrene were used to study the correlations between sorption/desorption isotherm nonlinearity and compositional data obtained from quantitative ¹³C solid-state DPMAS NMR spectroscopy for soil and peat organic matter with or without lipids. Sorption experiments were conducted using a batch equilibration method. Desorption experiments were carried out immediately following the sorption experiments by three successive decant-refill cycles. Hysteresis was observed in all samples. Nonlinear sorption behavior was increased by removal of lipids from the NOM. The hysteresis index, obtained from the ratio of the Freundlich exponents (N values) for the desorption and sorption isotherms, was lower in the lipid-extracted NOM samples than in the same samples without lipid extraction. The relationship between the extent of hysteresis and the characteristics of the ¹³C DPMAS NMR spectra indicates that altering NOM composition through lipid extraction not only increased the proportion of aromatic-C content, but also increased sorption/desorption hysteresis. Our data also suggest that the hysteresis index is negatively related to aromaticity.     

Pollutants and the health of green sea turtles resident to an urbanized estuary in San Diego, CA

Rapid expansion of coastal anthropogenic development means that critical foraging and developmental habitats often occur near highly polluted and urbanized environments. Although coastal contamination is widespread, the impact this has on long-lived vertebrates like the green turtle (Chelonia mydas) is unclear because traditional experimental methods cannot be applied. We coupled minimally invasive sampling techniques with health assessments to quantify contaminant patterns in a population of green turtles resident to San Diego Bay, CA, a highly urbanized and contaminated estuary. Several chemicals were correlated with turtle size, suggesting possible differences in physiological processes or habitat utilization between life stages. With the exception of mercury, higher concentrations of carapace metals as well as 4,4′-dichlorodiphenyldichloroethylene (DDE) and γ chlordane in blood plasma relative to other sea turtle studies raises important questions about the chemical risks to turtles resident to San Diego Bay. Mercury concentrations exceeded immune function no-effects thresholds and increased carapace metal loads were correlated with higher levels of multiple health markers. These results indicate immunological and physiological effects studies are needed in this population. Our results give insight into the potential conservation risk contaminants pose to sea turtles inhabiting this contaminated coastal habitat, and highlight the need to better manage and mitigate contaminant exposure in San Diego Bay.     

Toxicity assessment of a common laundry detergent using the freshwater flagellate Euglena gracilis

Synthetic detergents are among the commonly used chemicals in everyday life. Detergents, reaching aquatic environments through domestic and municipal wastewater, can cause many different effects in aquatic organisms. The present study was aimed at the toxicity evaluation of a commonly used laundry detergent, Ariel, using the freshwater flagellate Euglena gracilis as a biotest organism. Different parameters of the flagellate like motility, swimming velocity, cell shape, gravitactic orientation, photosynthesis and concentration of light harvesting pigments were used as end points for the toxicity assessment. No Observed Effect Concentration (NOEC) and EC₅₀ values were calculated for the end point parameters at four different incubation times, i.e. 0, 6, 24 and 72 h. After 72 h incubation, swimming velocity of the cells was found to be the most sensitive parameter giving NOEC and EC₅₀ values of 10.8 and 34 mg L⁻¹, respectively. After 72 h exposure to the detergent, chlorophyll a and total carotenoids were significantly decreased in cultures treated with Ariel at concentrations of 50 mg L⁻¹ and above while chlorophyll b significantly decreased at concentrations above 750 mg L⁻¹. The maximum inhibitory effect on the quantum yield of photosystem II was observed after 24 h exposure and thereafter a recovery trend was observed. Motility, gravitaxis and cell shape were strongly impaired immediately upon exposure to the detergent, but with increasing exposure time these parameters showed acclimatization to the stress and thus the NOEC values obtained after 72 h were higher than those immediately after exposure.     

Air quality assessment by tree bark biomonitoring in urban, industrial and rural environments of the Rhine Valley: PCDD/Fs, PCBs and trace metal evidence

Tree barks were used as biomonitors to evaluate past atmospheric pollution within and around the industrial zones of Strasbourg (France) and Kehl (Germany) in the Rhine Valley. The here estimated residence time for trace metals, PCBs and PCDD/Fs in tree bark is >10 years. Thus, all pollution observed by tree bark biomonitoring can be older than 10 years. The PCB baseline concentration (sum of seven PCB indicators (Σ₇PCB_ind)) determined on tree barks from a remote area in the Vosges mountains is 4 ng g⁻¹ and corresponds to 0.36 × 10⁻³ ng toxic equivalent (TEQ) g⁻¹ for the dioxin-like PCBs (DL-PCBs). The northern Rhine harbor suffered especially from steel plant, waste incinerator and thermal power plant emissions. The polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/Fs) concentrations analyzed in tree barks from this industrial area range between 392 and 1420 ng kg⁻¹ dry-weight (dw) corresponding to 3.9 ng TEQ_PCDD/Fs kg⁻¹ to 17.8 ng TEQ_PCDD/Fs kg⁻¹, respectively. Highest PCDD/F values of 7.2 ng TEQ kg⁻¹ to 17.8 ng TEQ kg⁻¹ have been observed close to and at a distance of <2 km southwest of the chemical waste incinerator. However, very close to this incinerator lowest TEQ dioxin-like PCB (TEQ_DL-PCB) values of 0.006 ng TEQ g⁻¹ have been found. On the other hand close to and southwest and northeast of the steel plant the values are comparatively higher and range between 0.011 ng TEQ g⁻¹ and 0.026 ng TEQ g⁻¹. However, even stronger Σ₇PCB_ind enrichments have been observed at a few places in the city center of Kehl, where ΣDL-PCB values of up to 0.11 ng TEQ g⁻¹ have been detected. These enrichments, however, are the result of ancient pollutions since recent long-term measurements at the same sites indicate that the atmospheric PCB concentrations are close to baseline. Emissions from an old landfill of waste and/or great fires might have been the reasons of these PCB enrichments. Other urban environments of the cities of Kehl and Strasbourg show significantly lower Σ₇PCB_ind concentrations. They suffer especially from road and river traffic and have typically Σ₇PCB_ind concentrations ranging from 11 ng g⁻¹ to 29 ng g⁻¹. The PCB concentration of 29 ng g⁻¹ has been found in tree bark close to the railway station of Strasbourg. Nevertheless, the corresponding TEQ_DL-PCB are low and range between 0.2 × 10⁻³ ng TEQ g⁻¹ and 7 × 10⁻³ ng TEQ g⁻¹. Samples collected near road traffic are enriched in Fe, Sb, Sn and Pb. Cd enrichments were found close to almost all types of industries. Rural environments not far from industrial sites suffered from organic and inorganic pollution. In this case, TEQ_DL-PCB values may reach up to 58 × 10⁻³ ng TEQ g⁻¹ and the corresponding V, Cr, Co, Ni, and Cd concentrations are comparatively high.     

Importance of heterocylic aromatic compounds in monitored natural attenuation for coal tar contaminated aquifers: A review

NSO heterocycles (HET) are typical constituents of coal tars. However, HET are not yet routinely monitored, although HET are relatively toxic coal tar constituents. The main objectives of the study is therefore to review previous studies and to analyse HET at coal tar polluted sites in order to assess the relevance of HET as part of monitored natural attenuation (MNA) or any other long-term monitoring programme. Hence, natural attenuation of typical HET (indole, quinoline, carbazole, acridine, methylquinolines, thiophene, benzothiophene, dibenzothiophene, benzofuran, dibenzofuran, methylbenzofurans, dimethylbenzofurans and xanthene) were studied at three different field sites in Germany. Compound-specific plume lengths were determined for all main contaminant groups (BTEX, PAH and HET). The results show that the observed plume lengths are site-specific and are above 250m, but less than 1000m. The latter, i.e. the upper limit, however mainly depends on the level of investigation, the considered compound, the lowest measured concentration and/or the achieved compound-specific detection limit and therefore cannot be unequivocally defined. All downstream contaminant plumes exhibited HET concentrations above typical PAH concentrations indicating that some HET are generally persistent towards biodegradation compared to other coal tar constituents, which results in comparatively increased field-derived half-lives of HET. Additionally, this study provides a review on physicochemical and toxicological parameters of HET. For three well investigated sites in Germany, the biodegradation of HET is quantified using the centre line method (CLM) for the evaluation of bulk attenuation rate constants. The results of the present and previous studies suggest that implementation of a comprehensive monitoring programme for heterocyclic aromatic compounds is relevant at sites, if MNA is considered in risk assessment and for remediation.     

Integrated evaluation of the performance of a more than seven year old permeable reactive barrier at a site contaminated with chlorinated aliphatic hydrocarbons (CAHs)

An important issue of concern for permeable reactive iron barriers is the long-term efficiency of the barriers due to the long operational periods required. Mineral precipitation resulting from the anaerobic corrosion of the iron filings and bacteria present in the barrier may play an important role in the long-term performance. An integrated study was performed on the Vapokon permeable reactive barrier (PRB) in Denmark by groundwater and iron core sample characterization. The detailed field groundwater sampling carried out from more than 75 well screens up and downstream the barrier showed a very efficient removal (>99%) for the most important CAHs (PCE, TCE and 1,1,1-TCA). However, significant formation of cis-DCE within the PRB resulted in an overall insufficient efficiency for cis-DCE removal. The detailed analysis of the upstream groundwater revealed a very heterogeneous spatial distribution of contaminant loading into the PRB, which resulted in that only about a quarter of the barrier system is treating significant loads of CAHs. Laboratory batch experiments using contaminated groundwater from the site and iron material from the core samples revealed that the aged iron material performed equally well as virgin granular iron of the same type based on determined degradation rates despite that parts of the cored iron material were covered by mineral precipitates (especially iron sulfides, carbonate green rust and aragonite). The PCR analysis performed on the iron core samples indicated the presence of a microbial consortium in the barrier. A wide range of species were identified including sulfate and iron reducing bacteria, together with Dehalococcoides and Desulfuromonas species indicating microbial reductive dehalogenation potential. The microbes had a profound effect on the performance of the barrier, as indicated by significant degradation of dichloromethane (which is typically unaffected by zero valent iron) within the barrier.     

Total fuel-cycle analysis of heavy-duty vehicles using biofuels and natural gas-based alternative fuels

Heavy-duty vehicles (HDVs) present a growing energy and environmental concern worldwide. These vehicles rely almost entirely on diesel fuel for propulsion and create problems associated with local pollution, climate change, and energy security. Given these problems and the expected global expansion of HDVs in transportation sectors, industry and governments are pursuing biofuels and natural gas as potential alternative fuels for HDVs. Using recent lifecycle datasets, this paper evaluates the energy and emissions impacts of these fuels in the HDV sector by conducting a total fuel-cycle (TFC) analysis for Class 8 HDVs for six fuel pathways: (1) petroleum to ultra low sulfur diesel; (2) petroleum and soyoil to biodiesel (methyl soy ester); (3) petroleum, ethanol, and oxygenate to e-diesel; (4) petroleum and natural gas to Fischer-Tropsch diesel; (5) natural gas to compressed natural gas; and (6) natural gas to liquefied natural gas. TFC emissions are evaluated for three greenhouse gases (GHGs) (carbon dioxide, nitrous oxide, and methane) and five other pollutants (volatile organic compounds, carbon monoxide, nitrogen oxides, particulate matter, and sulfur oxides), along with estimates of total energy and petroleum consumption associated with each of the six fuel pathways. Results show definite advantages with biodiesel and compressed natural gas for most pollutants, negligible benefits for e-diesel, and increased GHG emissions for liquefied natural gas and Fischer-Tropsch diesel (from natural gas).     

A mathematical model for the interactive behavior of sulfate-reducing bacteria and methanogens during anaerobic digestion

Anaerobic degradation of waste involves different classes of microorganisms, and there are different types of interactions among them for substrates, terminal electron acceptors, and so on. A mathematical model is developed based on the mass balance of different substrates, products, and microbes present in the system to study the interaction between methanogens and sulfate-reducing bacteria (SRB). The performance of major microbial consortia present in the system, such as propionate-utilizing acetogens, butyrate-utilizing acetogens, acetoclastic methanogens, hydrogen-utilizing methanogens, and SRB were considered and analyzed in the model. Different substrates consumed and products formed during the process also were considered in the model. The experimental observations and model predictions showed very good prediction capabilities of the model. Model prediction was validated statistically. It was observed that the model-predicted values matched the experimental data very closely, with an average error of 3.9%.     

In situ chemical oxidation: Lessons learned at multiple sites

This paper compiles a detailed set of in situ chemical oxidation (ISCO) lessons learned pertaining to design, execution, and safety based on global experiences over the last 20 years. While the benefits of a “correct” application are known (e.g., cost effectiveness, speed, permanence of treatment), history also provides examples of a variety of “incorrect” applications. These provide an opportunity to highlight recurring themes that resulted in failures. ISCO is, and will continue to provide, an important remedial tool for site remediation, particularly as a component of a multifaceted approach for addressing large and complex sites. Future success, however, requires an objective understanding of both the benefits and the limitations of the technology. The ability to learn from the mistakes of the past provides an opportunity to eliminate, or at least minimize, them in the future. Over the last 25 years of ISCO application, process understanding and knowledge have improved and evolved. This paper combines a thorough discussion of lessons learned through decades of ISCO implementation throughout all aspects of ISCO projects with an analysis of changes to the ISCO remediation market. By discussing the interplay of these two themes and providing recommendations from collective lessons learned, we hope to improve the future of safe, cost‐effective, and successful applications of ISCO.     

Probabilistic Flood Inundation Forecasting Using Rating Curve Libraries

One approach for performing uncertainty assessment in flood inundation modeling is to use an ensemble of models with different conceptualizations, parameters, and initial and boundary conditions that capture the factors contributing to uncertainty. However, the high computational expense of many hydraulic models renders their use impractical for ensemble forecasting. To address this challenge, we developed a rating curve library method for flood inundation forecasting. This method involves pre‐running a hydraulic model using multiple inflows and extracting rating curves, which prescribe a relation between streamflow and stage at various cross sections along a river reach. For a given streamflow, flood stage at each cross section is interpolated from the pre‐computed rating curve library to delineate flood inundation depths and extents at a lower computational cost. In this article, we describe the workflow for our rating curve library method and the Rating Curve based Automatic Flood Forecasting (RCAFF) software that automates this workflow. We also investigate the feasibility of using this method to transform ensemble streamflow forecasts into local, probabilistic flood inundation delineations for the Onion and Shoal Creeks in Austin, Texas. While our results show water surface elevations from RCAFF are comparable to those from the hydraulic models, the ensemble streamflow forecasts used as inputs to RCAFF are the largest source of uncertainty in predicting observed floods.