Dendroremediation of trinitrotoluene (TNT) part 1: Literature overview and research concept

BACKGROUND, AIM AND SCOPE: For decades, very large areas of former military sites have been contaminated diffusely with the persistent nitroaromatic explosive 2,4,6-trinitrotoluene (TNT). The recalcitrance of the environmental hazard TNT is to a great extent due to its particulate soil existence, which leads to slow but continuous leaching processes. Although improper handling during the manufacture of TNT seems to be a problem of the past in developed countries, environmental deposition of TNT and other explosives is still going on unfortunately, resulting from thousands of unexploded ordnance or low order explosions at munitions test areas and at current battlefields. OBJECTIVE: Sustainable phytoremediation strategies for explosives in Germany, which intend to use trees to decontaminate soil and groundwater ('dendroremediation'), have to consider that most of the former German military sites are already covered with woodlands, mainly with conifer stands. Therefore, parallel investigation of the remediation potential is necessary for both of the selected hybrids of fast growing broadleaf trees, which are waiting for planting and forest conifers, which have already proven for decades that they are able to grow on explosive contaminated sites. MAIN FEATURES: A short literature review is given regarding phytoremediation of TNT with herbaceous plants and some general aspects of dendroremediation are discussed. Furthermore, an overview of our TNT-dendroremediation research network is introduced, which has the strategic goal to make dendroremediation more calculable for a series of potent trees for site-adapted in situ application and for the assessment of tree remediation potentials in natural attenuation processes. RESULTS AND DISCUSSION: Some of our methods, results and conclusions yet unpublished are presented. For a preliminary calculation of area-related annual TNT dendroremediation potential of five-year-old trees, the following values were assessed: Salix EW-13 6.0, Salix EW-20 8.5, Populus ZP-007 4.2, Betula pendula 5.2, Picea abies 1.9 and Pinus sylvestris 0.8 g m(-2) a(-1). For a 45-year-old spruce forest, an annual natural attenuation potential of 4.2 g TNT m(-2) a(-1) was found. CONCLUSION, RECOMMENDATIONS AND PERSPECTIVE: Our main results deliver quantitative proposals for dendroremediation strategies in situ and provide decision aids. Also aspects of growth of raw materials for energy production are considered. Our dendroremediation research concept for TNT and its congeners can be easily completed for other trees of interest and it can also be applied to herbaceous plants. Knowing the current bottlenecks of phytoremediation and considering the known environmental behaviour of other contaminants, elements of our methodological approach may be easily adapted to those pollutant groups, e.g. for pesticides, pharmaceuticals, PAHs, chlorinated recalcitrants and, with some restrictions, to inorganics and to multiple contaminations. Our dynamical dendrotolerance test systems will help to predict tree growth on polluted areas. To provide some light into the black box of TNT dendroremediation, experimental data regarding the uptake, distribution and degradation of [14C]-TNT in mature tree tissues will be reported in the second part of this publication.     

Natural attenuation/phytoremediation in the vadose zone of a former industrial sludge basin

The natural attenuation of polyaromatic hydrocarbons (PAHs) in the vadose zone of a naturally revegetated former industrial sludge basin (0.45 ha) was examined. This was accomplished by comparing the concentration of 16 PAH contaminants present in sludge collected below the root zone of plants with contaminants present at 3 shallower depths within the root zone. Chemical analysis of 240 samples from 60 cores showed the average concentration of total and individual PAHs in the 0-30 cm, 30-60 cm, and bottom of the root zone strata were approximately 10, 20, and 50%, respectively, of the 16, 800 ppm average total PAH concentration in deep non-rooted sludge. Statistically significant differences in average PAH concentrations were observed between each strata studied and the non-rooted sludge except for the concentrations of acenaphthene and chrysene present at the bottom of the root zone in comparison to sludge values. The rooting depth of the vegetation growing in the basin was dependent on both vegetation type and plant age. Average rooting depths for trees, forbs (herbaceous non-grasses), and grasses were 90, 60, and 50 cm, respectively. The deepest root systems observed (100-120 cm) were associated with the oldest (12-14 year-old) mulberry trees. Examination of root systems and PAH concentrations at numerous locations and depths within the basin indicated that plant roots and their microbially active rhizospheres fostered PAH disappearance; including water insoluble, low volatility compounds, i.e. benzo(a)pyrene and benzo(ghi)perylene. The reduced concentration of PAHs in the upper strata of this revegetated former sludge basin indicated that natural attenuation had occurred. This observation supports the concept that through appropriate planting and management practices (phytoremediation) it will be possible to accelerate, maximize, and sustain natural processes, whereby even the most recalcitrant PAH contaminants (i.e. benzo(a)pyrene) can be remediated over time.     

Changes in enantiomeric fraction as evidence of natural attenuation of mecoprop in a limestone aquifer

Natural attenuation of the chiral pesticide mecoprop [2-(2-methyl-4-chlorophenoxy)propionic acid] has been studied by determining changes in its enantiomeric fraction in different redox environments down gradient of a landfill in the Lincolnshire Limestone. Previous studies have shown that mecoprop degrades predominantly aerobically and that differences in the biological behaviour of the two enantiomers will change their relative proportions during biodegradation. Originally deposited as a racemic mixture, there has been no change in the enantiomeric fraction in the most polluted part of the landfill plume where conditions are sulphate reducing/methanogenic. In the nitrate-reducing zone, the proportion of (S)-mecoprop increases, suggesting preferential degradation of (R)-mecoprop; while in the aerobic zone, the proportion of (R)-mecoprop increases, suggesting faster degradation of (S)-mecoprop. Mecoprop persistence in the confined Lincolnshire Limestone further downdip is explained by inhibition of degradation in sulphate-reducing conditions, which develop naturally. Laboratory microcosm experiments using up to 10 mg l(-1) of mecoprop confirm these inferences and show that under aerobic conditions, (S)-mecoprop and (R)-mecoprop degrade with zero-order kinetics at rates of 1.90 and 1.32 mg l(-1) day(-1), respectively. Under nitrate-reducing conditions (S)-mecoprop does not degrade, but (R)-mecoprop degrades with zero-order kinetics at 0.65 mg l(-1) day(-1) to produce a stoichiometric equivalent amount of 4-chloro-2-methylphenol. This metabolite only degrades when the (R)-mecoprop has disappeared. The addition of nitrate to a dormant iron-reducing microcosm devoid of nitrate stimulated anaerobic degradation of (R)-mecoprop after a lag period of 21 days. There was no evidence for enantiomeric inversion. The study demonstrates the sensitivity of changes in enantiomeric fraction for detecting natural attenuation, and reveals subtle differences in mecoprop degradation in different redox environments within the Lincolnshire Limestone aquifer.     

IMPACT ASSESSMENT MODEL FOR CLEAR WATER FISHES EXPOSED TO EXCESSIVELY CLOUDY WATER1

ABSTRACT: A new type of empirical model described here enables real time assessment of impacts caused by excessive water cloudiness as a function of (a) reduced visual clarity (excessive cloudiness) and (b) duration of exposure to cloudy conditions, in fisheries or fish life stages adapted to life in clear water ecosystems. This model takes the familiar form used in earlier suspended sediment dose effect models where z is severity of ill effect (SEV), x is duration of exposure (h), y is black disk sighting range (y BD, m)—a measure of water clarity, a is the intercept, and b and c are slope coefficients. As calibrated in this study the model is Severity of ill effect is ranked on a 15‐step scale that ranges from 0 to 14, where zero represents nil effect and 14 represents 100 percent mortality. This model, based on peer consultation and limited meta analysis of peer reviewed reports, accomplishes the following: (a) identifies the threshold of the onset of ill effects among clear water fishes; (b) postulates the rate at which serious ill effects are likely to escalate as a function of reduced visual clarity and persistence; (c) provides a context (the “visual clarity” matrix, with its cell coordinates) to share and compare information about impacts as a function of visual clarity “climate” (d) demonstrates changes in predator prey interactions at exposures greater than and less than the threshold of direct ill effects; (e) calibrates trout reactive distance (cm) as function of water clarity in the form where y represents reactive distance (cm) and x represents visual clarity (black disk sighting range, cm), and where a and b are intercept and slope respectively, such that (f) identifies black disk sighting range, in meters, and its reciprocal, beam attenuation, as preferred monitoring variables; and (g) provides two additional optical quality variables (Secchi disk extinction distance and turbidity) which, suitably calibrated as they have been in this study, expand the range of monitoring options in situations in which the preferred technology—beam attenuation equipment or black disk sighting equipment—is unavailable or impractical to use. This new model demonstrates the efficacy of peer collaboration and defines new research horizons for its refinement.     

Effects of humic acid coatings on phenanthrene sorption to black carbon

Black carbon (BC) can strongly adsorb hydrophobic organic compounds (HOCs).The HOC sorption to coated BC could be attenuated in soil and sediment compared with that of the parent BC.To study the potential causes of the sorption attenuation,humic acid (HA) and BC were isolated.Phenanthrene (PHE) was selected as the representative of HOCs.BC was coated with the precipitated HA.The PHE sorption to the HA-coated BC was determined.The HA coatings on BC could result in the significant sorption attenuation of PHE to BC.The attenuation varied in different HA origin and was positively correlated to the aromaticity of HA.The attenuation could be explained by the direct competition between HA and PHE for the available sorption sites on BC and the reduction of the available sorption sites as a result of the pore blockage of BC caused by the HA coatings.Therefore,the HA coatings on BC was one potential cause of the attenuation of HOC sorption to BC in soil and sediment.     

Factors affecting nitrate distribution in shallow groundwater under a beef farm in South Eastern Ireland

Groundwater contamination was characterised using a methodology which combines shallow groundwater geochemistry data from 17 piezometers over a 2 yr period in a statistical framework and hydrogeological techniques. Nitrate–N (NO₃-N) contaminant mass flux was calculated across three control planes (rows of piezometers) in six isolated plots. Results showed natural attenuation occurs on site although the method does not directly differentiate between dilution and denitrification. It was further investigated whether NO₃-N concentration in shallow groundwater (<5 m below ground level) generated from an agricultural point source on a 4.2 ha site on a beef farm in SE Ireland could be predicted from saturated hydraulic conductivity (K_sat) measurements, ground elevation (m Above Ordnance Datum), elevation of groundwater sampling (screen opening interval) (m AOD) and distance from a dirty water point pollution source. Tobit regression, using a background concentration threshold of 2.6 mg NO₃-N L⁻¹ showed, when assessed individually in a step wise procedure, K_sat was significantly related to groundwater NO₃-N concentration. Distance of the point dirty water pollution source becomes significant when included with K_sat in the model. The model relationships show areas with higher K_sat values have less time for denitrification to occur, whereas lower K_sat values allow denitrification to occur. Areas with higher permeability transport greater NO₃-N fluxes to ground and surface waters. When the distribution of Cl⁻ was examined by the model, K_sat and ground elevation had the most explanatory power but K_sat was not significant pointing to dilution having an effect. Areas with low NO₃ concentration and unaffected Cl⁻ concentration points to denitrification, low NO₃ concentration and low Cl⁻ chloride concentration points to dilution and combining these findings allows areas of denitrification and dilution to be inferred. The effect of denitrification is further supported as mean groundwater NO₃-N was significantly (P < 0.05) related to groundwater N₂/Ar ratio, redox potential (Eh), dissolved O₂ and N₂ and was close to being significant with N₂O (P = 0.08). Calculating contaminant mass flux across more than one control plane is a useful tool to monitor natural attenuation. This tool allows the identification of hot spot areas where intervention other than natural attenuation may be needed to protect receptors.     

Lagrangian Sampling for Emerging Contaminants Through an Urban Stream Corridor in Colorado1

Abstract: Recent national concerns regarding the environmental occurrence of emerging contaminants (ECs) have catalyzed a series of recent studies. Many ECs are released into the environment through discharges from wastewater treatment plants (WWTPs) and other sources. In 2005, the U.S. Geological Survey and the City of Longmont initiated an investigation of selected ECs in a 13.8‐km reach of St. Vrain Creek, Colorado. Seven sites were sampled for ECs following a Lagrangian design; sites were located upstream, downstream, and in the outfall of the Longmont WWTP, and at the mouths of two tributaries, Left Hand Creek and Boulder Creek (which is influenced by multiple WWTP outfalls). Samples for 61 ECs in 16 chemical use categories were analyzed and 36 were detected in one or more samples. Of these, 16 have known or suspected endocrine‐disrupting potential. At and downstream from the WWTP outfall, detergent metabolites, fire retardants, and steroids were detected at the highest concentrations, which commonly exceeded 1 μg/l in 2005 and 2 μg/l in 2006. Most individual ECs were measured at concentrations less than 2 μg/l. The results indicate that outfalls from WWTPs are the largest but may not be the sole source of ECs in St. Vrain Creek. In 2005, high discharge was associated with fewer EC detections, lower total EC concentrations, and smaller EC loads in St. Vrain Creek and its tributaries as compared with 2006. EC behavior differed by individual compound, and some differences between sites could be attributed to analytical variability or to other factors such as physical or chemical characteristics or distance from contributing sources. Loads of some ECs, such as diethoxynonylphenol, accumulated or attenuated depending on location, discharge, and distance downstream from the WWTP, whereas others, such as bisphenol A, were largely conservative. The extent to which ECs in St. Vrain Creek affect native fish species and macroinvertebrate communities is unknown, but recent studies have shown that fish respond to very low concentrations of ECs, and further study on the fate and transport of these contaminants in the aquatic environment is warranted.     

Characterizing As(III,V) adsorption by soils surrounding ash disposal facilities

Leachate derived from unlined coal ash disposal facilities is a potential anthropogenic source of arsenic to the environment. To establish a theoretical framework for predicting attenuation of arsenic by soils subject to ash landfill leachate, which is typically enriched in calcium and sulfate, the adsorption of As(V) and As(III) was characterized from 1 mM CaSO₄ for 18 soils obtained down-gradient from three ash landfill sites and representing a wide range in soil properties. As(V) consistently exhibited an order of magnitude greater adsorption than As(III). As(V) adsorption was best described by coupling pH with 15 s DCB-Fe (R² = 0.851,  = 0.001), although pH coupled to clay, DCB-Fe, or DCB-Al also generated strong correlations. For As(III), pH coupled to Ox–Fe (R² = 0.725,  = 0.001) or Ox–Fe/Al (R² = 0.771,  = 0.001) provided the best predictive relationships. Ca²⁺ induced increases in As(V) adsorption whereas sulfate suppressed both As(V) and As(III) adsorption. Attenuation of arsenic from ash leachate agreed well with adsorption measured from 1 mM CaSO₄ suggesting that the use of 1 mM CaSO₄ in laboratory adsorption tests is a reasonable approach for estimating arsenic behavior in soils surrounding ash landfills. We also showed that the impact of leachate-induced changes in soil pH over time may not be significant for As(V) adsorption at pH < 7; however, As(III) adsorption may be impacted over a wider pH range especially if phyllosilicate clays contribute significantly to adsorption. The benefits and limitations of predicting arsenic mobility using linearized adsorption coefficients estimated from nonlinear adsorption isotherms or from the relationships generated in this study are also discussed.     

Occurrence and attenuation of specific organic compounds in the groundwater plume at a former gasworks site

The changing contaminant pattern with travelled distance was investigated in the anaerobic groundwater plume downstream from an extended zone containing residual NAPL at a former gas manufacturing plant. With increasing distance, O- and N-heterocyclic aromatic compounds are enriched in the plume relative to the usually assessed coal tar constituents (poly- and monocyclic aromatic compounds). In a first approximation, the overall concentration decrease of the investigated compounds follows a first order overall decay. The half life distance in the plume downgradient from the source varied between 20 m for benzene and up to 167-303 m for alkyl-naphthalenes. Acenaphthene is degraded only within about 50 m downstream from the source area, then its concentration remains constant (ca. 180 microg/l) and far above the legal limit. Dimethyl-benzofurans were the most recalcitrant among all compounds which could be quantified with the analytical method available. The overall groundwater contamination in the plume is seriously underestimated if only BTEX and 16-EPA-PAHs are monitored.     

双起电方式静电电荷衰减测试仪

在分析了静电电荷衰减测试原理的基础上,提出了以AT89C51单片机为核心组成测试系统,来实现测试自动化的设计方案,设计了具体的硬件结构,重点阐述了测试仪的高压源,信号调理电路,A／D转换电路等的实现,并采用C51进行软件编程。该测试仪工作可靠,具有良好的测量精度和灵敏度,实现测试自动化的同时,很好地提高了测试的准确性。