Reed beds receiving industrial sludge containing nitroaromatic compounds

Goal, Scope and Background Sweden has prohibited the deposition of organic waste since January, 2005. Since 1 million tons of sludge is produced every year in Sweden and the capacity for incineration does not fill the demands, other methods of sludge management have to be introduced to a larger degree. One common method in the USA and parts of Europe is the use of wetlands to treat wastewater and sewage sludge. The capacity of reed beds to affect the toxicity of a complex mixture of nitroaromatics in sludge, however, is not fully elucidated. In this study, an industrial sludge containing explosives and pharmaceutical residues was therefore treated in artificial reed beds and the change in toxicity was studied. Nitroaromatic compounds, which are the main ingredients of many pharmaceuticals and explosives, are well known to cause cytotoxicity and genotoxicity. Recently performed studies have also showed that embryos of zebrafish (Danio rerio) are sensitive to nitroaromatic compounds. Therefore, we tested the sludge passing through constructed wetlands in order to detect any changes in levels of embryotoxicity, genotoxicity and dioxin-like activity (AhR-agonists). We also compared unplanted and planted systems in order to examine the impact of the root system on the fate of the toxicants. Methods An industrial sludge containing a complex mixture of nitroaromatics was added daily to small-scale constructed wetlands (vertical flow), both unplanted and planted with Phragmites australis. Sludge with an average dry weight of 1.25%, was added with an average hydraulic loading rate of 1.2 L/day. Outgoing water was collected daily and stored at −20°C. The artificial wetland sediment was Soxhlet extracted, followed by clean-up with multi-layer silica, or extracted by ultrasonic treatment, yielding one organic extract and one water extract of the same sample. Genotoxicity of the extracts was measured according to the ISO protocol for the umu-C genotoxicity assay (ISO/TC 147/SC 5/WG9 N8), using Salmonella typhimurium TA1535/pSK1002 as test organism. Embryotoxicity and teratogenicity were studied using the fish egg assay with zebrafish (Danio rerio) and the dioxin-like activity was measured using the DR-CALUX assay. Chemical analyses of nitroaromatic compounds were performed using Solid Phase Micro Extraction (SPME) and GC-MS. Results Organic extracts of the bed material showed toxic potential in all three toxicity tests after two years of sludge loading. There was a difference between the planted and the unplanted beds, where the toxicity of organic extracts overall was higher in the bed material from the planted beds. The higher toxicity of the planted beds could have been caused by the higher levels of total carbon in the planted beds, which binds organic toxicants, and by enrichment caused by lower volumes of outgoing water from the planted beds. Discussion Developmental disorders were observed in zebrafish exposed directly in contact to bed material from unplanted beds, but not in fish exposed to bed material from planted beds. Hatching rates were slightly lower in zebrafish exposed to outgoing water from unplanted beds than in embryos exposed to outgoing water from planted beds. Genotoxicity in the outgoing water was below detection limit for both planted and unplanted beds. Most of the added toxicants via the sludge were unaccounted for in the outgoing water, suggesting that the beds had toxicant removal potential, although the mechanisms behind this remain unknown. Conclusions During the experimental period, the beds received a sludge volume (dry weight) of around three times their own volume. In spite of this, the toxicity in the bed material was lower than in the sludge. Thus, the beds were probably able to actually decrease the toxicity of the added, sludge-associated toxicants. When testing the acetone extracts of the bed material, the planted bed showed a higher toxicity than the unplanted beds in all three toxicity tests. The toxicity of water extracts from the unplanted beds, detected by the fish egg assay, were higher than the water extracts from the planted beds. No genotoxicity was detected in outgoing water from either planted or unplanted beds. All this together indicates that the planted reed beds retained semi-lipophilic acetone-soluble toxic compounds from the sludge better than the unplanted beds, which tended to leak out more of the water soluble toxic compounds in the outgoing water. The compounds identified by SPME/GC in the outgoing water were not in sufficient concentrations to have caused induction in the genotoxicity test. Recommendations and Perspectives This study has pointed out the benefits of using constructed wetlands receiving an industrial sludge containing a complex mixture of nitroaromatics to reduce toxicity in the outgoing water. The water from planted, constructed wetlands could therefore be directed to a recipient without further cleaning. The bed material should be investigated over a longer period of time in order to evaluate potential accumulation and leakage prior to proper usage or storage. The plants should be investigated in order to examine uptake and possible release when the plant biomass is degraded. This article has been developed on the basis of a presentation given at the Annual meeting of SETAC Europe German Language Branch 2004 in Aachen. ESS-Submission Editor: Dr. Ludek Blaha (blaha@recetox.muni.cz)     

Metal accumulation in earthworms inhabiting floodplain soils

The main factors contributing to variation in metal concentrations in earthworms inhabiting floodplain soils were investigated in three floodplains differing in inundation frequency and vegetation type. Metal concentrations in epigeic earthworms showed larger seasonal variations than endogeic earthworms. Variation in internal levels between sampling intervals were largest in earthworms from floodplain sites frequently inundated. High and low frequency flooding did not result in consistent changes in internal metal concentrations. Vegetation types of the floodplains did not affect metal levels in Lumbricus rubellus, except for internal Cd levels, which were positively related to the presence of organic litter. Internal levels of most essential metals were higher in spring. In general, no clear patterns in metal uptake were found and repetition of the sampling campaign will probably yield different results.     

Eutrophication of mangroves linked to depletion of foliar and soil base cations

There is growing concern that increasing eutrophication causes degradation of coastal ecosystems. Studies in terrestrial ecosystems have shown that increasing the concentration of nitrogen in soils contributes to the acidification process, which leads to leaching of base cations. To test the effects of eutrophication on the availability of base cations in mangroves, we compared paired leaf and soil nutrient levels sampled in Nypa fruticans and Rhizophora spp. on a severely disturbed, i.e. nutrient loaded, site (Mahakam delta) with samples from an undisturbed, near-pristine site (Berau delta) in East Kalimantan, Indonesia. The findings indicate that under pristine conditions, the availability of base cations in mangrove soils is determined largely by salinity. Anthropogenic disturbances on the Mahakam site have resulted in eutrophication, which is related to lower levels of foliar and soil base cations. Path analysis suggests that increasing soil nitrogen reduces soil pH, which in turn reduces the levels of foliar and soil base cations in mangroves.     

CO2 Capture and Storage with Leakage in an Energy-Climate Model

Geological CO₂ capture and storage (CCS) is among the main near-term contenders for addressing the problem of global climate change. Even in a baseline scenario, with no comprehensive international climate policy, a moderate level of CCS technology is expected to be deployed, given the economic benefits associated with enhanced oil and gas recovery. With stringent climate change control, CCS technologies will probably be installed on an industrial scale. Geologically stored CO₂, however, may leak back to the atmosphere, which could render CCS ineffective as climate change reduction option. This article presents a long-term energy scenario study for Europe, in which we assess the significance for climate policy making of leakage of CO₂ artificially stored in underground geological formations. A detailed sensitivity analysis is performed for the CO₂ leakage rate with the bottom-up energy systems model MARKAL, enriched for this purpose with a large set of CO₂ capture technologies (in the power sector, industry, and for the production of hydrogen) and storage options (among which enhanced oil and gas recovery, enhanced coal bed methane recovery, depleted fossil fuel fields, and aquifers). Through a series of model runs, we confirm that a leakage rate of 0.1%/year seems acceptable for CCS to constitute a meaningful climate change mitigation option, whereas one of 1%/year is not. CCS is essentially no option to achieve CO₂ emission reductions when the leakage rate is as high as 1%/year, so more reductions need to be achieved through the use of renewables or nuclear power, or in sectors like industry and transport. We calculate that under strict climate control policy, the cumulative captured and geologically stored CO₂ by 2100 in the electricity sector, when the leakage rate is 0.1%/year, amounts to about 45,000 MtCO₂. Only a little over 10,000 MtCO₂ cumulative power-generation-related emissions are captured and stored underground by the end of the century when the leakage rate is 1%/year. Overall marginal CO₂ abatement costs increase from a few €/tCO₂ today to well over 150 €/tCO₂ in 2100, under an atmospheric CO₂ concentration constraint of 550 ppmv. Carbon costs in 2100 turn out to be about 40 €/tCO₂ higher when the annual leakage rate is 1%/year in comparison to when there is no CO₂ leakage. Irrespective of whether CCS deployment is affected by gradual CO₂ seepage, the annual welfare loss in Europe induced by the implementation of policies preventing “dangerous anthropogenic interference with the climate system” (under our assumption, implying a climate stabilisation target of 550 ppmv CO₂ concentration) remains below 0.5% of GDP during the entire century.

Assessing the Relative Importance of Spatial Variability in Emissions Versus Landscape Properties in Fate Models for Environmental Exposure Assessment of Chemicals

Multimedia mass balance models differ in their treatment of spatial resolution from single boxes representing an entire region to multiple interconnected boxes with varying landscape properties and emission intensities. Here, model experiments were conducted to determine the relative importance of these two main factors that cause spatial variation in environmental chemical concentrations: spatial patterns in emission intensities and spatial differences in environmental conditions. In the model, experiments emissions were always to the air compartment. It was concluded that variation in emissions is in most cases the dominant source of variation in environmental concentrations. It was found, however, that variability in environmental conditions can strongly influence predicted concentrations in some cases, if the receptor compartments of interest are soil or water—for water concentrations particularly if a chemical has a high octanol–air partition coefficient (K _oa). This information will help to determine the required level of spatial detail that suffices for a specific regulatory purpose.     

The Use of Atmospheric Dispersion Models in Risk Assessment Decision Support Systems for Pesticides

In the evaluation of potentially adverse effects oforganic chemicals such as pesticides on theenvironment the atmosphere may play an important role.After its release to the atmosphere the chemical willbe transported/dispersed in the atmosphere and finallyit will be removed either by atmospheric-chemicaldestruction or by deposition to the underlying soil orsurface water. In a risk assessment decision supportsystem both ambient concentrations and depositionfluxes must be known to evaluate the risk of directexposure (inhalation) or the risk of soil and watercontamination caused by deposition. This paperdiscusses the use of atmospheric dispersion models insuch risk assessment decision support systems.     

Mapping nitrate leaching to upper groundwater in the sandy regions of The Netherlands, using conceptual knowledge

The European Community asks its Member States to provide a comprehensive and coherent overview of their groundwater chemical status. It is stated that simple conceptual models are necessary to allow assessments of the risks of failing to meet quality objectives. In The Netherlands two monitoring networks (one for agriculture and one for nature) are operational, providing results which can be used for an overview. Two regression models, based upon simple conceptual models, link measured nitrate concentrations to data from remote sensing images of land use, national forest inventory, national cattle inventory, fertiliser use statistics, atmospheric N deposition, soil maps and weather monitoring. The models are used to draw a nitrate leaching map and to estimate the size of the area exceeding the EU limit value in the early 1990s. The 95% confidence interval for the fraction nature and agricultural areas where the EU limit value for nitrate (50 mg/l) was exceeded amounted to 0.77–0.85 while the lower 97.5% confidence limit for the fraction agricultural area where the EU limit value was exceeded amounted to 0.94. Although the two conceptual models can be regarded as simple, the use of the models to give an overview was experienced as complex.     

Xeno-estrogenic compounds in precipitation

The exposure to some chemicals can lead to hormone disrupting effects. Presently, much attention is focused on so-called xeno-estrogens, synthetic compounds that interact with hormone receptors causing a number of reactions that eventually lead to effects related to reproduction and development. The current study was initiated to investigate the presence of a number of such compounds in precipitation as a follow-up on a previous study in which pesticide concentrations in air and precipitation were determined. Rainwater samples were collected at about 50 locations in The Netherlands in a four week period. The samples were analysed for bisphenol-A, alkylphenols and alkylphenol ethoxylates, phthalates, flame retardants and synthetic musk compounds. The results clearly indicated the presence of these compounds in precipitation. The concentrations ranged from the low ng l(-1) range for flame retardants to several thousands of ng l(-1) for the phthalates. Bisphenol-A was found in 30% of the samples in concentrations up to 130 ng l(-1), while alkylphenols and alkylphenol ethoxylates were found in virtually all locations in concentrations up to 920 ng l(-1) for the individual compounds. Phthalates were by far the most abundant xeno-estrogens in the precipitation samples and were found in every sample. Di-isodecyl phthalate was found in a surprisingly high concentration of almost 100 000 ng l(-1). Polybrominated flame retardants were found in the low ng l(-1) range and generally in less than 20% of the samples. Noticeable was the finding of hexabromocyclododecane, a replacement for the polybrominted diphenyl ethers at one location in a concentration of almost 2000 ng l(-1). Finally, as expected, synthetic musk compounds were detected in almost all samples. This is especially true for the polycyclic musks HHCB and AHTN. Nitro musks were found, but only on a few locations. Kriging techniques were used to calculate precipitation concentrations in between actual sampling locations to produce contour plots for a number of compounds. These plots clearly show located emission sources for a number of compounds such as bisphenol-A, nonylphenol ethoxylate, phthalates and AHTN. On the contrary, the results for HHCB and some phthalates indicated diffuse emission patterns, probably as the result of the use of consumer products containing these compounds.