A European survey of atmospheric heavy metal deposition in 2000-2001

The background, administration and current status of the monitoring programme "European Survey of Atmospheric Heavy Metal Deposition" is described. All European states are invited to join the survey 2000-2001. The co-ordination and responsibility for the survey will gradually be transferred from the Nordic Council of Ministers to the International Cooperative Programme on Effects of Air Pollution on Natural Vegetation and Crops (ICP Vegetation).     

Retention of arsenic on hydrous ferric oxides generated by electrochemical peroxidation

Electrochemical peroxidation (ECP), an emerging remediation technology, with direct electric current applied to steel electrode and small addition of H2O2, was used to remove As(III) from contaminated aqueous solutions. Bench scale experiments were conducted to evaluate the sorption and distribution of arsenic between the soluble and solid state hydrous ferric oxides (HFO) formed as part of the ECP process. ECP was effective in removing arsenic from the aqueous solution, with >98% of the applied As(III) adsorbed on HFO. Removal was complete within 3 min of ECP treatment and apparently independent of the initial pH of the water (3.5-9.5). In the absence of H2O2 more As(III) was adsorbed by solid state iron at pH 9.5 than at 3.5 (2600 vs. 1750 microg l(-1)). Thus H2O2 was crucial to oxidize As(III) to As(V) which is more strongly retained by HFO. Removal of As was not significantly affected by the concentration of H2O2 or by current processing time. The optimal operating conditions were pH < 6.5, H2O2 concentration of 10 mg l(-1) and current process time not exceeding 3 min. X-ray diffraction (XRD), diffuse-reflectance infrared Fourier transform (DRIFT) spectroscopy and transmission electron microscopy (TEM) were applied to study the HFO deposits. The XRD data indicated the prevalence of poorly ordered Fe minerals in the suspended ECP solids with a dominance of 5 line ferrihydrite in the absence of H2O2. At pH 3.5 and with 100 mg H2O2 l(-1), akaganeite was formed, whereas an incipient hematitic phase, reflection at 0.39 nm, occurred at pH 6.5. DRIFT data indicate that both As(III) and As(V) were specifically adsorbed onto HFO at acid and neutral pH. TEM observations indicated the presence of spherical shape ferrihydrite and provided evidence for possible formation of subrounded hematite and acicular shape goethite.     

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     

Using polymer mats to biodegrade atrazine in groundwater: laboratory column experiments

Large-scale column experiments were undertaken to evaluate the potential of in situ polymer mats to deliver oxygen into groundwater to induce biodegradation of the pesticides atrazine, terbutryn and fenamiphos contaminating groundwater in Perth, Western Australia. The polymer mats, composed of woven silicone (dimethylsiloxane) tubes and purged with air, were installed in 2-m-long flow-through soil columns. The polymer mats proved efficient in delivering dissolved oxygen to anaerobic groundwater. Dissolved oxygen concentrations increased from <0.2 mg l(-1) to approximately 4 mg l(-1). Degradation rates of atrazine in oxygenated groundwater were relatively high with a zero-order rate of 240-380 microg l(-1) or a first-order half-life of 0.35 days. Amendment with an additional carbon source showed no significant improvement in biodegradation rates, suggesting that organic carbon was not limiting biodegradation. Atrazine degradation rates estimated in the column experiments were similar to rates determined in laboratory culture experiments, using pure cultures of atrazine-mineralising bacteria. No significant degradation of terbutryn or fenamiphos was observed under the experimental conditions within the time frames of the study. Results from these experiments indicate that remediation of atrazine in a contaminated aquifer may be achievable by delivery of oxygen using an in situ polymer mat system.     

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.     

Induction of PAH-catabolism in mushroom compost and its use in the biodegradation of soil-associated phenanthrene

This paper describes the induction of phenanthrene-catabolism within Phase II mushroom compost resulting from its incubation with (1) phenanthrene, and (2) PAH-contaminated soil. Respirometers measuring mineralization of freshly added 14C-9-phenanthere were used to evaluate induction of phenanthrene-catabolism. Where pure phenanthrene (spiked at a concentration of 400 mg kg(-1) wet wt.) was used to induce phenanthrene-catabolism in compost, induction was measurable, with maximal mineralization observed after 7 weeks phenanthrene-compost contact time. Where PAH-contaminated soil was used to induce phenanthrene-catabolism in un-induced compost, induction was observed after 5 weeks soil-compost contact time. Microcosm-scale amelioration of soil contaminated with 14C-phenanthrene (aged in soil for 516 days prior to incubation with compost) indicated that both induced (using pure phenanthrene) and uninduced Phase II mushroom composts were equally able to promote degradation of this soil-associated contaminant. After 111 days incubation time, 42.7 +/- 6.3% loss of soil-associated phenanthrene was observed in the induced-compost soil mixture, while 36.7 +/- 2.9% loss of soil-associated phenanthrene was observed in the uninduced-compost soil mixture. These results are notable as they indicate that while pre-induction of phenanthrene-catabolism within compost is possible, it does not significantly increase the extent of degradation when the compost is used to ameliorate phenanthrene-contaminated soil. Thus, compost could be used directly in the amelioration of contaminated land i.e. without pre-induction of catabolism.     

Tolerance to,and avoidance of,hypoxia by the penaeid shrimp (Metapenaeus ensis)

Aquatic hypoxia caused by eutrophication may lead to mass mortality of valuable living resources such as fish and shrimp. However, there is little information on the hypoxic tolerance of penaeid shrimp, and whether they are able to avoid hypoxia. In laboratory experiments, LC50, LT50 and heart beats per minute were determined for juvenile Metapenaeus ensis at 0.5, 1.0, 2.0 and 6.0 mg O2 l(-1). The 8-h LC50, for DO was 0.77 mg O2 l(-1), while the LT50 at 0.5 mg O2 l(-1) was 399 min. Heart beat rate significantly declined when DO fell below 1.0 mg O2 l(-1). When confronted with a gradient of dissolved oxygen, M. ensis were able to avoid hypoxic areas and move to oxygenated water. M. ensis appeared to be sensitive to hypoxia, and their ability to detect and avoid hypoxia may enhance their survival in habitats where hypoxia may occur.     

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.     

UV-VIS spectroscopy of 2,4,6-trinitrotoluene-hydroxide reaction

Contamination of groundwater, surface water and soil by explosives has occurred at military sites throughout the world as a result of manufacture of explosive compounds, assembly of munitions, and deployment of explosives containing devices. Due to the adverse effects of explosives on humans and other natural receptors, a low cost means of decontaminating these areas of contamination is needed. Base-induced transformation of explosives has shown promise as a rapid, low cost, and minimally resource-intensive technology for detoxifying explosives in soil and water. In order to understand the reaction mechanism, a reaction mixture of 2:1:1 (water:2,4,6-trinitrotoluene (TNT):1 N KOH) was analyzed by UV/VIS spectrometry from 190 to 1,100 nm. Time course measurements were conducted at 25, 20, 15, and 12 degrees C. A factor analysis program was used to analyze the spectral data. Principal component analysis indicated that six principal components explained the spectra to within experimental error, with four factors explaining the majority of the variance. Test spectral vectors for four components were developed, including TNT, two intermediates, and the final product, and were tested against the abstract vectors. Two possible reaction mechanisms were suggested and tested to explain the spectral data.     

Hexabromocyclododecane diastereomers in fish and suspended particulate matter from selected European waters—trend monitoring and environmental quality standard compliance

The brominated flame retardant hexabromocyclododecane (HBCD) was monitored in fish and sediment (from one lake) or suspended particulate matter (SPM; from five rivers) at European freshwater sites to study the effects of reduction measures implemented by HBCD producers and users in recent years. Bream (Abramis brama) were sampled annually between 2007 and 2013 in the rivers Götaälv/SE, Rhône/FR, Western Scheldt/NL, Mersey/UK, and Tees/UK and in Lake Belau/DE. Sediment/SPM was taken every second year between 2008 and 2014. HBCD was analyzed by LC/MS/MS allowing the determination of the alpha-, beta-, and gamma-diastereomers. For most sites, a decrease in ∑HBCD was observed in fish (e.g., in the Rhône and Western Scheldt by about 80 and 60%, respectively, with significantly decreasing trends, p < 0.01). In the Rhône, HBCD also decreased in SPM. At the sampling site in the Tees which was impacted by a former HBCD point source, fish HBCD levels decreased only after a major flood event in 2013. While fish data indicate a decline in environmental HBCD concentrations at most sites with diffuse emissions, SPM data were less conclusive. The European environmental quality standard for HBCD in fish of 167 μg kg^?1 wet weight was met by all fish samples in 2013.