Engineered in situ bioremediation of a petroleum hydrocarbon-contaminated aquifer: assessment of mineralization based on alkalinity, inorganic carbon and stable carbon isotope balances

A concept is proposed to assess in situ petroleum hydrocarbon mineralization by combining data on oxidant consumption, production of reduced species, CH₄, alkalinity and dissolved inorganic carbon (DIC) with measurements of stable isotope ratios. The concept was applied to a diesel fuel contaminated aquifer in Menziken, Switzerland, which was treated by engineered in situ bioremediation. In the contaminated aquifer, added oxidants (O₂ and NO₃⁻) were consumed, elevated concentrations of Fe(II), Mn(II), CH₄, alkalinity and DIC were detected and the DIC was generally depleted in ¹³C compared to the background. The DIC production was larger than expected based on the consumption of dissolved oxidants and the production of reduced species. Stable carbon isotope balances revealed that the DIC production in the aquifer originated mainly from microbial petroleum hydrocarbon mineralization, and that geochemical reactions such as carbonate dissolution produced little DIC. This suggests that petroleum hydrocarbon mineralization can be underestimated if it is determined based on concentrations of dissolved oxidants and reduced species.     

Biodegradation potential of MTBE in a fractured chalk aquifer under aerobic conditions in long-term uncontaminated and contaminated aquifer microcosms

The potential for aerobic biodegradation of MTBE in a fractured chalk aquifer is assessed in microcosm experiments over 450 days, under in situ conditions for a groundwater temperature of 10 °C, MTBE concentration between 0.1 and 1.0 mg/L and dissolved O₂ concentration between 2 and 10 mg/L. Following a lag period of up to 120 days, MTBE was biodegraded in uncontaminated aquifer microcosms at concentrations up to 1.2 mg/L, demonstrating that the aquifer has an intrinsic potential to biodegrade MTBE aerobically. The MTBE biodegradation rate increased three-fold from a mean of 6.6 ± 1.6 μg/L/day in uncontaminated aquifer microcosms for subsequent additions of MTBE, suggesting an increasing biodegradation capability, due to microbial cell growth and increased biomass after repeated exposure to MTBE. In contaminated aquifer microcosms which also contained TAME, MTBE biodegradation occurred after a shorter lag of 15 or 33 days and MTBE biodegradation rates were higher (max. 27.5 μg/L/day), probably resulting from an acclimated microbial population due to previous exposure to MTBE in situ. The initial MTBE concentration did not affect the lag period but the biodegradation rate increased with the initial MTBE concentration, indicating that there was no inhibition of MTBE biodegradation related to MTBE concentration up to 1.2 mg/L. No minimum substrate concentration for MTBE biodegradation was observed, indicating that in the presence of dissolved O₂ (and absence of inhibitory factors) MTBE biodegradation would occur in the aquifer at MTBE concentrations (ca. 0.1 mg/L) found at the front of the ether oxygenate plume. MTBE biodegradation occurred with concomitant O₂ consumption but no other electron acceptor utilisation, indicating biodegradation by aerobic processes only. However, O₂ consumption was less than the stoichiometric requirement for complete MTBE mineralization, suggesting that only partial biodegradation of MTBE to intermediate organic metabolites occurred. The availability of dissolved O₂ did not affect MTBE biodegradation significantly, with similar MTBE biodegradation behaviour and rates down to ca. 0.7 mg/L dissolved O₂ concentration. The results indicate that aerobic MTBE biodegradation could be significant in the plume fringe, during mixing of the contaminant plume and uncontaminated groundwater and that, relative to the plume migration, aerobic biodegradation is important for MTBE attenuation. Moreover, should the groundwater dissolved O₂ concentration fall to zero such that MTBE biodegradation was inhibited, an engineered approach to enhance in situ bioremediation could supply O₂ at relatively low levels (e.g. 2–3 mg/L) to effectively stimulate MTBE biodegradation, which has significant practical advantages. The study shows that aerobic MTBE biodegradation can occur at environmentally significant rates in this aquifer, and that long-term microcosm experiments (100s days) may be necessary to correctly interpret contaminant biodegradation potential in aquifers to support site management decisions.     

Microbial growth and transport in porous media under denitrification conditions: experiments and simulations

Soil column experiments were conducted to study bacterial growth and transport in porous media under denitrifying conditions. The study used a denitrifying microbial consortium isolated from aquifer sediments sampled at the U.S. Department of Energy's Hanford site. One-dimensional, packed-column transport studies were conducted under two substrate loading conditions. A detailed numerical model was developed to predict the measured effluent cell and substrate concentration profiles. First-order attachment and detachment models described the interphase exchange processes between suspended and attached biomass. Insignificantly different detachment coefficient values of 0.32 and 0.43 day⁻¹, respectively, were estimated for the high and low nitrate loading conditions (48 and 5 mg l⁻¹ NO₃, respectively). Comparison of these values with those calculated from published data for aerobically growing organisms shows that the denitrifying consortium had lower detachment rate coefficients. This suggests that, similar to detachment rates in reactor-grown biofilms, detachment in porous media may increase with microbial growth rate. However, available literature data are not sufficient to confirm a specific analytical model for predicting this growth dependence.     

Microbial characterization of nitrification in a shallow, nitrogen-contaminated aquifer, Cape Cod, Massachusetts and detection of a novel cluster associated with nitrifying Betaproteobacteria

Groundwater nitrification is a poorly characterized process affecting the speciation and transport of nitrogen. Cores from two sites in a plume of contamination were examined using culture-based and molecular techniques targeting nitrification processes. The first site, located beneath a sewage effluent infiltration bed, received treated effluent containing O₂ (> 300 µM) and NH₄⁺ (51–800 µM). The second site was 2.5 km down-gradient near the leading edge of the ammonium zone within the contaminant plume and featured vertical gradients of O₂, NH₄⁺, and NO₃⁻ (0–300, 0–500, and 100–200 µM with depth, respectively). Ammonia- and nitrite-oxidizers enumerated by the culture-based MPN method were low in abundance at both sites (1.8 to 350 g^− 1 and 33 to 35,000 g^− 1, respectively). Potential nitrifying activity measured in core material in the laboratory was also very low, requiring several weeks for products to accumulate. Molecular analysis of aquifer DNA (nested PCR followed by cloning and 16S rDNA sequencing) detected primarily sequences associated with the Nitrosospira genus throughout the cores at the down-gradient site and a smaller proportion from the Nitrosomonas genus in the deeper anoxic, NH₄⁺ zone at the down-gradient site. Only a single Nitrosospira sequence was detected beneath the infiltration bed. Furthermore, the majority of Nitrosospira-associated sequences represent an unrecognized cluster. We conclude that an uncharacterized group associated with Nitrosospira dominate at the geochemically stable, down-gradient site, but found little evidence for Betaproteobacteria nitrifiers beneath the infiltration beds where geochemical conditions were more variable.     

Mineralization of PAHs in coal-tar impacted aquifer sediments and associated microbial community structure investigated with FISH

The microbial community structure and mineralization of polycyclic aromatic hydrocarbons (PAHs) in a coal-tar contaminated aquifer were investigated spatially using fluorescence in situ hybridization (FISH) and in laboratory-scale incubations of the aquifer sediments. DAPI-detected microbial populations in the contaminated sediments were three orders of magnitude greater than nearby uncontaminated sediments, suggesting growth on coal-tar constituents in situ. Actinobacteria, beta- and gamma-Proteobacteria, and Flavobacteria dominated the in situ aerobic (>1 mg l(-1) dissolved oxygen) microbial community, whereas sulfate-reducing bacteria comprised 37% of the microbial community in the sulfidogenic region of the aquifer. Rapid mineralization of naphthalene and phenanthrene were observed in aerobic laboratory microcosms and resulted in significant enrichment of beta- and gamma-Proteobacteria potentially explaining their elevated presence in situ. Firmicutes, Flavobacteria, alpha-Proteobacteria, and Actinobacteria were also enriched in the mineralization assays, but to a lesser degree. Nitrate- and sulfate-limited mineralization of naphthalene in laboratory microcosms occurred to a small degree in aquifer sediments from locations where groundwater chemistry indicated nitrate- and sulfate-reduction, respectively. Some iron-limited mineralization of naphthalene and phenanthrene was also observed in sediments originating near groundwater measurements of elevated ferrous iron. The results of this study suggest that FISH may be a useful tool for providing a much needed link between laboratory microcosms and groundwater measurements made in situ necessary to better demonstrate the potential for natural attenuation at complex PAH contaminated sites.     

Consequences of nitrate leaching following stem-only harvesting of Swedish forests are dependent on spatial scale

Short-term increases in soil solution nitrate (NO₃⁻) concentration are often observed after forest harvest, even in N-limited systems. We model NO₃⁻ leaching below the rooting zone as a function of site productivity. Using national forest inventories and published estimates of N attenuation in rivers and the riparian zone, we estimate effects of stem-only harvesting on NO₃⁻ leaching to groundwater, surface waters and the marine environment. Stem-only harvesting is a minor contributor to NO₃⁻ pollution of Swedish waters. Effects in surface waters are rapidly diluted downstream, but can be locally important for shallow well-waters as well as for the total amount of N reaching the sea. Harvesting adds approximately 8 Gg NO₃-N to soil waters in Sweden, with local concentrations up to 7 mg NO₃-N l⁻¹. Of that, ∼3.3 Gg reaches the marine environment. This is ∼3% of the overall Swedish N load to the Baltic.     

Influence of detergent formulation on nutrient movement through sand columns simulating mound and conventional septic system drainfields

The effects of phosphate (P) and zeolite (Z) -built detergents on leaching of N and P through sand columns simulating septic system drainfields were examined in laboratory columns. To simulate mound septic system drainfields, paired sets of columns were dosed intermittently with septic tank effluent from households using P- or Z-built detergent. Two other paired sets of columns were flooded with P- or Z-effluent to simulate new conventional septic system drainfields; after clogging mats or “crusts” developed at infiltration surface, the subsurfaces of the columns were aerated to simulate mature (crusted) conventional septic system drainfields. NO₃ loading in leachate was 1.1 times higher and ortho-P loading was 4.3 times lower when columns were dosed with Z- than with P-effluent. Dosed columns removed P poorly; total phosphorus (TP) loading in leachate was 81 and 19 g m⁻² yr⁻¹ with P- and Z-effluent, respectively. In flooded columns 1.3, 2.0 and 1.8 times more NH₄, organic nitrogen (ON) and total nitrogen (TN) respectively, were leached with Z- than with P-effluent; NO₃ leaching was similar. Flooded columns removed P efficiently; TP leached through flooded systems was 2.5 and 1.4 g m⁻² yr⁻¹ with P- and Z effluent, respectively. Crusted columns fed Z-effluent leached 1.2, 2.6, 1.4 and 2.1 times more NH₄, NO₃, ON and TN, respectively, than those with P-effluent but 1.8 times less TP. Crusted columns removed P satisfactorily: 8.2 and 4.6 g m⁻² yr⁻¹ TP with P- and Z-effluent, respectively. The P-built detergent substantially improves the efficiency of N removal with satisfactory P removal in columns simulating conventional septic system drainfield. Simultaneous removal of N and P under flooded conditions might be explained by precipitation of struvite-type minerals. Dosed system drainfields were less efficient in removing N and P compared to flooded and crusted system drainfelds.     

Natural and anthropogenic factors affecting the groundwater quality in the Nandong karst underground river system in Yunan, China

The Nandong Underground River System (NURS) is located in a typical karst agriculture dominated area in the southeast Yunnan Province, China. Groundwater plays an important role for social and economical development in the area. However, with the rapid increase in population and expansion of farm land, groundwater quality has degraded. 42 groundwater samples collected from springs in the NURS showed great variation of chemical compositions across the study basin. With increased anthropogenic contamination in the area, the groundwater chemistry has changed from the typical Ca–HCO₃ or Ca (Mg)–HCO₃ type in karst groundwater to the Ca–Cl (+ NO₃) or Ca (Mg)–Cl (+ NO₃), and Ca–Cl (+ NO₃ + SO₄) or Ca (Mg)–Cl (+ NO₃ + SO₄) type, indicating increases in NO₃⁻, Cl⁻ and SO₄²⁻ concentrations that were caused most likely by human activities in the region. This study implemented the R-mode factor analysis to investigate the chemical characteristics of groundwater and to distinguish the natural and anthropogenic processes affecting groundwater quality in the system. The R-mode factor analysis together with geology and land uses revealed that: (a) contamination from human activities such as sewage effluents and agricultural fertilizers; (b) water–rock interaction in the limestone-dominated system; and (c) water–rock interaction in the dolomite-dominated system were the three major factors contributing to groundwater quality. Natural dissolution of carbonate rock (water–rock interaction) was the primary source of Ca²⁺ and HCO₃⁻ in groundwater, water–rock interaction in dolomite-dominated system resulted in higher Mg²⁺ in the groundwater, and human activities were likely others sources. Sewage effluents and fertilizers could be the main contributor of Cl⁻, NO₃⁻, SO₄²⁻, Na⁺ and K⁺ to the groundwater system in the area. This study suggested that both natural and anthropogenic processes contributed to chemical composition of groundwater in the NURS, human activities played the most important role, however.     

Transport of Escherichia coli and solutes during waste water infiltration in an urban alluvial aquifer

Recharge of waste water in an unconsolidated poorly sorted alluvial aquifer is a complex process, both physically and hydrochemically. The aim of this paper is to analyse and conceptualise vertical transport mechanisms taking place in an urban area of extensive wastewater infiltration by analysing and combining the water balance, the microbial (Escherichia coli) mass balance, and the mass balance for dissolved solutes. For this, data on sediment characteristics (grain size, organic carbon, reactive iron, and calcite), groundwater levels, and concentrations of E. coli in groundwater and waste water were collected. In the laboratory, data on E. coli decay rate coefficients, and on bacteria retention characteristics of the sediment were collected via column experiments. The results indicated that shallow groundwater, at depths of 50 m below the surface, was contaminated with E. coli concentrations as high as 10(6) CFU/100 mL. In general, E. coli concentrations decreased only 3 log units from the point of infiltration to shallow groundwater. Concentrations were lower at greater depths in the aquifer. In laboratory columns of disturbed sediments, bacteria removal was 2-5 log units/0.5 cm column sediment. Because of the relatively high E. coli concentrations in the shallow aquifer, transport had likely taken place via a connected network of pores with a diameter large enough to allow bacterial transport instead of via the sediment matrix, which was inaccessible for bacteria, as was clear from the column experiments. The decay rate coefficient was determined from laboratory microcosms to be 0.15 d(-1). Assuming that decay in the aquifer was similar to decay in the laboratory, then the pore water flow velocity between the point of infiltration and shallow groundwater, coinciding with a concentration decrease of 3 log units, was 0.38 m/d, and therefore, transport in this connected network of pores was fast. According to the water balance of the alluvial aquifer, determined from transient groundwater modelling, groundwater flow in the aquifer was mainly in vertical downward direction, and therefore, the mass balance for dissolved solutes was simulated using a 1D transport model of a 200 m column of the Quaternary Alluvium aquifer. The model, constructed with PHREEQC, included dual porosity, and was able to adequately simulate removal of E. coli, cation-exchange, and nitrification. The added value of the use of E. coli in this study was the recognition of relatively fast transport velocities occurring in the aquifer, and the necessity to use the dual porosity concept to investigate vertical transport mechanisms. Therefore, in general and if possible, microbial mass balances should be considered more systematically as an integral part of transport studies.     

Nocturnal NO3 radical chemistry in Houston,TX

Radical chemistry in the nocturnal urban boundary layer is dominated by the nitrate radical, NO₃, which oxidizes hydrocarbons and, through the aerosol uptake of N₂O₅, indirectly influences the nitrogen budget. The impact of NO₃ chemistry on polluted atmospheres and urban air quality is, however, not well understood, due to a lack of observations and the strong impact of vertical stability of the boundary layer, which makes nocturnal chemistry highly altitude dependent.Here we present long-path DOAS observations of the vertical distribution of the key nocturnal species O₃, NO₂, and NO₃ during the TRAMP experiment in Summer 2006 in Houston, TX. Our observations confirm the altitude dependence of nocturnal chemistry, which is reflected in the concentration profiles of all trace gases at night. In contrast to other study locations, NO₃ chemistry in Houston is dominated by industrial emissions of alkenes, in particular of isoprene, isobutene, and sporadically 1,3-butadiene, which are responsible for more than 70% of the nocturnal NO₃ loss. The nocturnally averaged loss of NO_x in the lowest 300 m of the Houston atmosphere is ～0.9 ppb h^?1, with little day-to-day variability. A comparison with the daytime NO_x loss shows that NO₃ chemistry is responsible for 16–50% of the NO_x loss in a 24-h period in the lowest 300 m of the atmosphere. The importance of the NO₃ + isoprene/1,3-butadiene reactions implies the efficient formation of organic nitrates and secondary organic aerosol at night in Houston.     

Sequential anaerobic-aerobic treatment of an aquifer contaminated by halogenated organics: field results

In situ, sequential, anaerobic to aerobic treatment of groundwater removed perchloroethene (PCE, 1.1 microM) and benzene (0.8 microM) from a contaminated aquifer. Neither aerobic nor anaerobic treatment alone successfully degraded both the chlorinated and non-chlorinated organic contaminants in the aquifer. After the sequential treatment, PCE, trichloroethene (TCE), vinyl chloride (VC), chloroethane (CA), and benzene were not detectable in groundwater. Desorption of residual aquifer contaminants was tested by halting the groundwater recirculation and analyzing the groundwater after 3 and 7 weeks. No desorption of the chlorinated contaminants or daughter products was observed in the treated portion of the aquifer. Sequential anaerobic to aerobic treatment was successful in remediating the groundwater at this test site and may have broad applications at other contaminated sites. Over the 4-year course of the project, the predominant microbial environment of the test site varied from aerobic to sulfate-reducing, to methanogenic, and back to aerobic conditions. Metabolically active microbial populations developed under all conditions, demonstrating the diversity and robustness of natural microbial flora in the aquifer.     

Removal of dissolved organic matter in municipal effluent with ozonation, slow sand filtration and nanofiltration as high quality pre-treatment option for artificial groundwater recharge

In the paper the combination process of ozonation, slow sand filtration (SSF) and nanofiltration (NF) was investigated with respect to dissolved organic matter (DOM) removal as high quality pre-treatment option for artificial groundwater recharge. With the help of ozonation leading to breakdown of the large organic molecules, SSF preferentially removes soluble microbial by-product-like substances and DOM with molecular weight (MW) less than 1.0 kDa. NF, however, removes aromatic, humic acid-like and fulvic acid-like substances efficiently and specially removes DOM with MW above 1.0 kDa. The residual DOM of the membrane permeate is dominated by small organics with MW 500 Da, which can be further reduced by the aquifer treatment, despite of the very low concentration. Consequently, the O₃/SSF/NF system offers a complementary process in DOM removal. Dissolved organic carbon (DOC) and trihalomethane formation potential (THMFP) can be reduced from 6.5 ± 1.1 to 0.7 ± 0.3 mg L⁻¹ and from 267 ± 24 to 52 ± 6 μg L⁻¹, respectively. The very low DOC concentration of 0.6 ± 0.2 mg L⁻¹ and THMFP of 44 ± 4 μg L⁻¹ can be reached after the aquifer treatment.     

Sequential coupling of bio-augmented permeable reactive barriers for remediation of 1,1,1-trichloroethane contaminated groundwater

Sequential coupling of high-density luffa sponge (HDLS) immobilized microorganism and permeable reactive barriers (IM Bio-PRBs) was superior to intimate coupling of free microorganism and permeable reactive barriers (FM Bio-PRBs) for remediation of 1,1,1-trichloroethane contaminated groundwater. IM Bio-PRBs had much better performance to removal 1,1,1-trichloroethane (1,1,1-TCA) and prevent the transport of 1,1,1-TCA and inorganic ions (NO₃^?, PO₄^3?, and SO₄^2?). The majority of them were prevented and accumulated in upgradient of IM Bio-PRBs. 1,1,1-TCA and inorganic ions in there contributed to the much faster growth of microorganism in upgradient aquifer. Therefore, the removal of 1,1,1-TCA and consumption of inorganic ions in upgradient of Bio-PRBs played a constructive role in reducing the processing load of following zero-valent iron (ZVI) PRBs and the negative effect of free microorganism cells (biological clogging) and inorganic ions (chemical clogging) on Bio-PRB permeability. In addition, IM Bio-PRBs were more conducive to accelerate the removal of 1,1,1-TCA in long-term remediation and 1,1,1-TCA residual concentration significantly lower than the safety standard of 0.2 mg L^?1. The change of terminal by-products of 1,1,1-TCA contaminated groundwater in Bio-PRBs showed that 1,1,1-TCA could be effectively de-chlorinated and mineralized in Bio-PRBs. The reductant H₂S (prolong the service life of ZVI-PRBs) was much more produced and utilized in IM Bio-PRBs. Taken together, sequentially coupled IM Bio-PRBs had a better overall performance, and its service life could be prolonged. It was a different design and idea to update conventional PRB remediation technology and theory.

     

Nitrate reduction during ground-water recharge, Southern High Plains, Texas

In arid and semi-arid environments, artificial recharge or reuse of wastewater may be desirable for water conservation, but NO₃⁻ contamination of underlying aquifers can result. On the semi-arid Southern High Plains (USA), industrial wastewater, sewage, and feedlot runoff have been retained in dozens of playas, depressions that focus recharge to the regionally important High Plains (Ogallala) aquifer. Analyses of ground water, playa-basin core extracts, and soil gas in an 860-km² area of Texas suggest that reduction during recharge limits NO₃⁻ loading to ground water. Tritium and Cl⁻ concentrations in ground water corroborate prior findings of focused recharge through playas and ditches. Typical δ¹⁵N values in ground water (>12.5‰) and correlations between δ¹⁵N and ln C_NO⁻3–N suggest denitrification, but O₂ concentrations ≥3.24 mg l⁻¹ indicate that NO₃⁻ reduction in ground water is unlikely. The presence of denitrifying and NO₃⁻-respiring bacteria in cores, typical soil–gas δ¹⁵N values <0‰, and decreases in NO₃⁻–N/Cl⁻ and SO₄²⁻/Cl⁻ ratios with depth in cores suggest that reduction occurs in the upper vadose zone beneath playas. Reduction may occur beneath flooded playas or within anaerobic microsites beneath dry playas. However, NO₃⁻–N concentrations in ground water can still exceed drinking-water standards, as observed in the vicinity of one playa that received wastewater. Therefore, continued ground-water monitoring in the vicinity of other such basins is warranted.     

Exposure to hazardous air pollutants along Oba Akran road, Lagos-Nigeria

We measured toxic air pollutants along Oba Akran road in Lagos to evaluate pedestrian exposure. PM₁₀, CO, O₃, NO₂, SO₂, CH₄, noise, wind velocity and temperature were measured simultaneously with portable analyzers. Our results showed that pedestrian exposure to PM₁₀ (with an average of 274.6 μg m⁻³ for all samples) and CO (with an average of 19.27 ppm for all samples) was relatively high. CO is a traffic-related pollutant, so the influence of the local traffic emissions on CO levels is strong. The high concentration of the PM₁₀ measured at the three environments also suggests that the traffic is a major source of ultrafine particles. The overall average concentrations for the 72-day experimental period for SO₂, NO₂ and O₃ are 101.2, 62.5 and 0.32 ppb respectively, all of which are below the US national ambient air quality standards. Strong traffic impacts can be observed from the concentrations of some of these pollutants measured in these three environments. Most clear is a reflection of diesel truck traffic activity rich in black carbon concentrations. The diurnal variation of O₃ and NO₂ also showed that NO₂ was depleted by photochemically formed O₃ during the day and replenished at night as O₃ was destroyed. A multivariate statistical analysis (Principal Component Analysis, Factor Analysis) has been applied to a set of data in order to determine the contribution of different sources. It was found that the main principal components, extracted from the air pollution data, were related to gasoline combustion, oil combustion and ozone interactions.     

Attenuation reactions in a multiple contaminated aquifer in Bitterfeld (Germany)

Large-scale contaminated sites with multiple contaminants in the groundwater present a challenge to risk assessment and remediation. Attenuation reactions take place in the subsurface and act to contain contaminants, but must be thoroughly investigated on a site-specific basis. Field data from monitoring wells at a contaminated industrial site in Bitterfeld, Germany, are presented and analyzed for evidence of the prevalent biodegradation reactions. The groundwater in the Tertiary aquifer is contaminated with large quantities of chlorinated aliphatic compounds, in addition to chlorobenzenes and BTEX. In this strictly anaerobic environment, geochemical indications for several microbial processes were found, including methanogenesis, sulfate and iron reduction as well as reductive dechlorination of the chlorinated hydrocarbons. Direct evidence for the latter degradation reaction was observed along the flowpath due to the appearance of intermediates and an increase in the degree of dechlorination.     

Is it possible to remediate a BTEX contaminated chalky aquifer by in situ chemical oxidation?

An industrial coating site in activity located on a chalky plateau, contaminated by BTEX (mainly xylenes, no benzene), is currently remediated by in situ chemical oxidation (ISCO). We present the bench scale study that was conducted to select the most appropriate oxidant. Ozone and catalyzed hydrogen peroxide (Fenton’s reaction) were discarded since they were incompatible with plant activity. Permanganate, activated percarbonate and activated persulfate were tested. Batch experiments were run with groundwater and groundwater-chalk slurries with these three oxidants. Total BTEX degradation in groundwater was reached with all the oxidants. The molar ratios [oxidant]:[Fe²⁺]:[BTEX] were 100:0:1 with permanganate, 100:100:1 with persulfate and 25:100:1 with percarbonate. Precipitation of either manganese dioxide or iron carbonate (siderite) occurred. The best results with chalk slurries were obtained with permanganate at the molar ratio 110:0:1 and activated persulfate at the molar ratio 110:110:1. To avoid precipitation, persulfate was also used without activation at the molar ratio 140:1. Natural Oxidant Demand measured with both oxidants was lower than 5% of initial oxidant contents. Activated percarbonate was not appropriate because of radical scavenging by carbonated media. Permanganate and persulfate were both effective at oxidant concentrations of ca 1 g kg⁻¹ with permanganate and 1.8 g kg⁻¹ with persulfate and adapted to site conditions. Activation of persulfate was not mandatory. This bench scale study proved that ISCO remediation of a chalky aquifer contaminated by mainly xylenes was possible with permanganate and activated or unactivated persulfate.     

Comparison of forest edge effects on throughfall deposition in different forest types

This study examined the influence of distance to the forest edge, forest type, and time on Cl⁻, SO₄²⁻, NO₃⁻, and NH₄⁺ throughfall deposition in forest edges. The forests were dominated by pedunculate oak, silver birch, or Corsican/Austrian pine, and were situated in two regions of Flanders (Belgium). Along transects, throughfall deposition was monitored at distances of 0-128 m from the forest edge. A repeated-measures analysis demonstrated that time, forest type, and distance to the forest edge significantly influenced throughfall deposition of the ions studied. The effect of distance to the forest edge depended significantly on forest type in the deposition of Cl⁻, SO₄²⁻, and NO₃⁻: the edge effect was significantly greater in pine stands than in deciduous birch and oak stands. This finding supports the possibility of converting pine plantations into oak or birch forests in order to mitigate the input of nitrogen and potentially acidifying deposition.     

Evidence for large average concentrations of the nitrate radical (NO3) in Western Europe from the HANSA hydrocarbon database

The nitrate radical (NO₃) was first measured in the atmosphere in the 1970s and suggestions were made that it could play a major role in oxidising many unsaturated hydrocarbons, such as those emitted from the biosphere. Analysis of the hydrocarbon mix over the North Atlantic Ocean suggested subsequently that the influence of NO₃ radical chemistry at night was even more extensive, being on a par with hydroxyl radical chemistry at some times of the year.The paper presents a detailed analysis of an extensive database of many nonmethane hydrocarbons collected at various sites around the North Sea in the mid 1990s during the HANSA project. By comparing the relative rates of oxidation of iso and normal pentane with that of toluene and benzene it clearly shows that the efficiency of NO₃ radical chemistry and hydroxyl radical chemistry over northwest Europe are similar in springtime and predicts an average nighttime NO₃ concentration of the order of 350 pptv, assuming an annual average OH concentration of 0.6×10⁶ cm⁻³. This value is very dependant on the average emission ratios of the different hydrocarbons and values between 200 and 600 pptv are possible. It is much larger than direct measurements made in Europe at the surface, but is of the same magnitude as concentrations measured recently from aircraft in the boundary layer over the northeast USA, and previously in vertical profiles by remote sounding over Europe.A simple analytical expression can be derived to calculate the NO₃ concentration at night with the only variables being ozone and the loss rate of N₂O₅, either to the ground or to aerosol surfaces. The concentrations of NO₃ calculated in this manner are similar to those derived from the analysis of the HANSA hydrocarbon database for typical conditions expected over Europe, but they are very dependant on the efficiency of the aerosol sink for N₂O₅.It is shown that NO₃ oxidation of many unsaturated hydrocarbons can indeed be more efficient than OH oxidation, especially at times of the year outside the summer season. Direct evidence for hydrocarbon oxidation by NO₃ radicals is shown by a series of peroxy radical measurements where the nighttime concentrations can be significantly higher than daytime concentrations in polluted air on occasion. Also the winter/summer (W/S) ratios of many unsaturated hydrocarbons are much lower than those expected from their removal purely by hydroxyl radical chemistry.The consequences of these findings are profound especially as satellite measurements of NO₂, a major precursor to NO₃, suggest that these high average concentrations of several hundred pptv could be widespread over most of the continents. This needs to be confirmed by direct in-situ measurement of nitrate radicals but it suggests a much larger role for NO₃ chemistry in the oxidation capacity of the atmosphere than realised hitherto.     

Air Quality Measurements from the Fresno Supersite

ABSTRACT

The Fresno Supersite intends to 1) evaluate non-routine monitoring methods, establishing their comparability with existing methods and their applicability to air quality planning, exposure assessment, and health effects studies; 2) provide a better understanding of aerosol characteristics, behavior, and sources to assist regulatory agencies in developing standards and strategies that protect public health; and 3) support studies that evaluate relationships between aerosol properties, co-factors, and observed health end-points. Supersite observables include in-situ, continuous, short-duration measurements of 1) PM_2.5, PM₁₀, and coarse (PM₁₀ minus PM_2.5) mass; 2) PM_2.5 SO₄ ^-2, NO₃ ^-, carbon, light absorption, and light extinction; 3) numbers of particles in discrete size bins ranging from 0.01 to ~10μm; 4) criteria pollutant gases (O₃, CO, NO_x); 5) reactive gases (NO₂, NO_y, HNO₃, peroxyacetyl nitrate [PAN], NH₃); and 6) single particle characterization by time-of-flight mass spectrometry. Field sampling and laboratory analysis are applied for gaseous and particulate organic compounds (light hydrocarbons, heavy hydrocarbons, carbonyls, polycyclic aromatic hydrocarbons [PAH], and other semi-volatiles), and PM_2.5 mass, elements, ions, and carbon. Observables common to other Supersites are 1) daily PM_2.5 24-hr average mass with Federal Reference Method (FRM) samplers; 2) continuous hourly and 5-min average PM_2.5 and PM₁₀ mass with beta attenuation monitors (BAM) and tapered element oscillating microbalances (TEOM); 3) PM_2.5 chemical specia-tion with a U.S. Environmental Protection Agency (EPA) speciation monitor and protocol; 4) coarse particle mass by dichotomous sampler and difference between PM₁₀ and PM_2.5 BAM and TEOM measurements; 5) coarse particle chemical composition; and 6) high sensitivity and time resolution scalar and vector wind speed, wind direction, temperature, relative humidity, barometric pressure, and solar radiation. The Fresno Supersite is coordinated with health and toxicological studies that will use these data in establishing relationships with asthma, other respiratory disease, and cardiovascular changes in human and animal subjects.