Natural attenuation of chlorinated solvents at Area 6, Dover Air Force Base: groundwater biogeochemistry

Monitored natural attenuation (MNA) has recently emerged as a viable groundwater remediation technology in the United States. Area 6 at Dover Air Force Base (Dover, DE) was chosen as a test site to examine the potential for MNA of tetrachloroethene (PCE) and trichloroethene (TCE) in groundwater and aquifer sediments. A "lines of evidence" approach was used to document the occurrence of natural attenuation. Chlorinated hydrocarbon and biogeochemical data were used to develop a site-specific conceptual model where both anaerobic and aerobic biological processes are responsible for the destruction of PCE, TCE, and daughter metabolites. An examination of groundwater biogeochemical data showed a region of depleted dissolved oxygen with elevated dissolved methane and hydrogen concentrations. Reductive dechlorination likely dominated in the anaerobic portion of the aquifer where PCE and TCE levels were observed to decrease with a simultaneous increase in cis-1,2-dichloroethene (cis-DCE), vinyl chloride (VC), ethene, and dissolved chloride. Near the anaerobic/ aerobic interface, concentrations of cis-DCE and VC decreased to below detection limits, presumably due to aerobic biotransformation processes. Therefore, the contaminant and daughter product plumes present at the site appear to have been naturally atteuated by a combination of active anaerobic and aerobic biotransformation processes.     

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.     

Metal accumulation in aquatic macrophytes from southeast Queensland,Australia

To determine the extent of metal accumulation in some aquatic macrophytes from contaminated urban streams in southeast Queensland, plants were sampled from six sites, along with contiguous sediments. In all, 15 different species were collected, the most common genera being Typha (Cattails or Bulrushes) and Persicaria (Knotweeds). Before heavy metal analysis, plants were further separated into various morphological tissues, and five selected samples were separated into various physiological tissues. The cadmium, copper, lead and zinc content of the plants were analysed using flames AAS. In general, plant roots exhibited higher metal concentrations than the contiguous sediments. Of the metals of interest, only for zinc was there a relatively clear pattern of increasing accumulation in aquatic macrophytes with increasing sediment metal concentrations. Comparison between morphological tissues of the sampled plants found that roots consistently presented higher metal concentrations than either the stems or leaves, however unlike previous studies, this investigation revealed no consistent trend of stems accumulating more metals than the leaves. For Typha spp., metal concentrations followed the order of roots > rhizomes > leaves, while for Persicaria spp. the order was roots > leaves > stems. The submerged species Myriophyllum aquaticum accumulated the highest levels of metals overall (e.g. Zn 4300 micrograms g-1 dry weight and Cd 6.5 micrograms g-1), and the emergent macrophytes also exhibited relatively high metal contents in their roots. The leaves of the submerged and floating-leafed species collected contained relatively high quantities of the four metals of interest, compared with the leaves of emergent aquatic macrophytes. In the Typha rhizome and Persicaria stem samples analysed for internal variation in metal content, there was a pattern of increasing metal concentrations towards the external sections of the stem, both for subterranean stems (rhizomes) and above-substrate stems. For Persicaria stems, no clear pattern was observed for cadmium and lead, the two metals investigated that are not required by plants for survival.     

Study of chlorothalonil photodegradation in natural waters and in the presence of humic substances

Photodegradation of chlorothalonil was studied in different natural waters (sea, river and lake) as well as in distilled water under natural and simulated solar irradiation. The effect of dissolved organic matter (DOM) such as humic and fulvic substances on the photodegradation rate of chlorothalonil was also studied in simulated sunlight. The presence of DOM enhanced the photodegradation of chlorothalonil with the exception of seawater. The kinetics were determined through gas chromatography electron capture detection (GC/ECD) and the photodegradation proceeds via pseudo-first-order reaction in all cases. Half-life ranged from 1 to 48 h. In natural and humic water chlorothalonil photodegradation gave rise to two different intermediates compared to distilled water demonstrating that the transformation of chlorothalonil depend on the constitution of the irradiated media and especially from DOM. The byproducts identified by GC/MS techniques were: chloro-1,3-dicyanobenzene, dichloro-1,3-dicyanobenzene, trichloro-1,3-dicyanobenzene and benzamide.     

Performance assessment of NAPL remediation in heterogeneous alluvium

Over the last few years, more than 40 partitioning interwell tracer tests (PITTs) have been conducted at many different sites to measure nonaqueous phase liquid (NAPL) saturations in the subsurface. While the main goal of these PITTs was to estimate the NAPL volume in the subsurface, some were specifically conducted to assess the performance of remedial actions involving NAPL removal. In this paper, we present a quantitative approach to assess the performance of remedial actions to recover NAPL that can be used to assess any NAPL removal technology. It combines the use of PITTs (to estimate the NAPL volume in the swept pore volume between injection and extraction wells of a test area) with the use of several cores to determine the vertical NAPL distribution in the subsurface. We illustrate the effectiveness of such an approach by assessing the performance of a surfactant/foam flood conducted at Hill Air Force Base, UT, to remove a TCE-rich NAPL from alluvium with permeability contrasts as high as one order of magnitude. In addition, we compare the NAPL volumes determined by the PITTs with volumes estimated through geostatistical interpolation of aquifer sediment core data collected with a vertical frequency of 5-10 cm and a lateral borehole spacing of 0.15 m. We demonstrate the use of several innovations including the explicit estimation of not only the errors associated with NAPL volumes and saturations derived from PITTs but also the heterogeneity of the aquifer sediments based upon permeability estimates. Most importantly, we demonstrate the reliability of the     

Preliminary background ozone concentrations in the mountain and coastal areas of Bulgaria

Urban and non-urban rural ozone (O3) concentrations are high in Bulgaria and often exceed the European AOT40 ecosystem as well as the AOT60 human health standards. This paper presents preliminary estimates to establish background, non-urban O3 concentrations for the southern region of Bulgaria. Ozone concentrations from three distinctly different sites are presented: a mountain site influenced by mountain-valley wind flow; a coastal site influenced by sea-breeze wind flow; and a 1700-m mountain peak site without 'local' wind flow characteristics. The latter offers the best estimate of 46-50 ppb for a background O3 level. The highest non-urban hourly value, 118 ppb, was measured at the mountain-valley site.     

Toxicity of methyl tert-butyl ether to marine organisms: ambient water quality criteria calculation

In response to increasing concerns over the detection of methyl tert-butyl ether (MTBE) in groundwater and surface water and its potential effects in aquatic ecosystems, industry and the United States Environmental Protection Agency (USEPA) began to collaborate in 1997 to develop aquatic toxicity databases sufficient to derive ambient water quality criteria for MTBE consistent with USEPA requirements. Acute toxicity data for seven marine species, chronic toxicity data for an invertebrate, and plant toxicity data were developed to complete the saltwater database. The species tested were Cyprinodon variegatus, Gasterosteus aculeatus, Callinectes sapidus, Mytilus galloprovincialis, Palaemonetes pugio, Rhepoxynius abronius, Americamysis bahia, and Skeletonema costatum. The toxicity tests were conducted in accordance with USEPA and American Society for Testing and Materials testing procedures and Good Laboratory Practice guidelines. Data developed from this study were consistent with existing data and showed that MTBE has low acute and chronic toxicity to the marine species tested. Based upon measured MTBE concentrations, acute effects were found to range from 166 mg MTBE/l for the grass shrimp to 1950 mg MTBE/l for marine mussel. The no-observed effect concentration for the reproduction and growth of mysids was 26 mg MTBE/l during the life cycle test. The toxicity of MTBE to saltwater organisms is comparable to its toxicity to the freshwater species tested. Reported MTBE concentrations in coastal waters are several orders of magnitude lower than concentrations observed to cause effects in marine organisms.     

As(III) removal from groundwaters using fixed-bed upflow bioreactors

The application of biological oxidation of iron and manganese, as a potential treatment method for the removal of arsenic from contaminated groundwaters, was examined in this paper. This method was based on the growth of certain species of indigenous bacteria, which are capable of oxidizing the soluble iron and manganese ions; the oxidized forms can be subsequently removed from the aqueous stream by over 97%, through their transformation to insoluble oxides and separation by a suitable filter medium. Arsenic was removed by around 80%, under certain conditions, which were found to be sufficient for Fe(II) removal (dissolved oxygen 2.7 mg/l, redox 280-290 mV, pH 7.2, U 8.25 m/h). The specific treatment technique presents several advantages towards conventional physicochemical treatment methods, such as enhanced coagulation or direct adsorption since: (a) it does not require the addition of other chemicals for oxidizing and removing As(III), (b) it does not require close monitoring of a breakthrough point, as in conventional column adsorption processes and (c) it could find application for the removal of, at least, three groundwater contaminants (Fe, Mn, As).     

Variation in CO2 assimilation rate induced by simulated dew waters with different sources of hydroxyl radical (*OH) on the needle surfaces of Japanese red pine (Pinus densifora Sieb. et Zucc.)

The hydroxyl radical (*OH) is generated in polluted dew on the needle surfaces of Japanese red pine (Pinus densiflora Sieb. et Zucc.). This free radical, which is a potent oxidant, is assumed to be a cause of ecophysiological disorders of declining trees on the urban-facing side of Mt. Gokurakuji, western Japan. Mists of *OH-generating N(III) (HNO2 and NO2-) and HOOH + Fe + oxalate solutions (50 and 100 microM, pH 5.1-5.4) simulating the dew water were applied to the foliage of pine seedlings grown in open-top chambers in the early morning. Needles treated with 100 microM N(III) tended to have a greater maximum CO2 assimilation rate (Amax), a greater stomatal conductance (g(s)) and a greater needle nitrogen content (Nneedle), suggesting that N(III) mist acts as a fertilizer rather than as a phytotoxin. On the other hand, needles treated with 100 microM HOOH + Fe + oxalate solution showed the smallest Amax, g(s), and Nneedle, suggesting that the combination of HOOH + Fe + oxalate caused a decrease in needle productivity. The effects of HOOH + Fe + oxalate mist on pine needles were very similar to the symptoms of declining trees at Mt. Gokurakuji.     

Bioaccumulation and elimination of 14C-lindane by Enchytraeus albidus in artificial (OECD) and a natural soil

Bioaccumulation and elimination of 14C-lindane in Enchytraeus albidus was studied in artificial OECD soil and a silty loam from an agricultural field in Central West Portugal. Results showed that enchytraeids were able to bioaccumulate the chemical with a kinetic pattern similar to that of earthworms: fast uptake within a few days and a biphasic elimination pattern. A 10 day period to study uptake was sufficient, but a few more days were probably necessary for elimination. Bioaccumulation was influenced by soil type. The authors suggest that higher organic matter (OM) content and also the higher content on sand particles in the OECD soil may have led to a faster elimination: hydrophobic chemicals tend to adsorb to OM being in this way less bioavailable and therefore less bioaccumulated having bioaccumulation factor value around 6 while in natural soil is 10; the sand could act as abrasive particles (helpers) in the elimination process leading to an elimination of 90% of the chemical in two days while in natural soil 67% was eliminated in the same period of time.