Risk assessment and prioritisation of contaminated sites on the catchment scale

Contaminated sites pose a significant threat to groundwater resources worldwide. Due to limited available resources a risk-based prioritisation of the remediation efforts is essential. Existing risk assessment tools are unsuitable for this purpose, because they consider each contaminated site separately and on a local scale, which makes it difficult to compare the impact from different sites. Hence a modelling tool for risk assessment of contaminated sites on the catchment scale has been developed. The CatchRisk screening tool evaluates the risk associated with each site in terms of its ability to contaminate abstracted groundwater in the catchment. The tool considers both the local scale and the catchment scale. At the local scale, a flexible, site specific leaching model that can be adjusted to the actual data availability is used to estimate the mass flux over time from identified sites. At the catchment scale, a transport model that utilises the source flux and a groundwater model covering the catchment is used to estimate the transient impact on the supply well. The CatchRisk model was tested on a groundwater catchment for a waterworks north of Copenhagen, Denmark. Even though data scarcity limited the application of the model, the sites that most likely caused the observed contamination at the waterworks were identified. The method was found to be valuable as a basis for prioritising point sources according to their impact on groundwater quality. The tool can also be used as a framework for testing hypotheses on the origin of contamination in the catchment and for identification of unknown contaminant sources.     

Is the growth stimulation by low doses of glyphosate sustained over time?

The herbicide, glyphosate, has been shown to stimulate growth in a range of species when applied at doses of 5-60 g a.e. ha⁻¹, corresponding to realistic spray drift events. This study investigates growth of shoot parameters over time to detect whether the glyphosate induced growth increase was sustained and had a final effect on reproduction. The results showed that an actual biomass growth rate increase took place within the first week after spraying with glyphosate doses <60 g a.e. ha⁻¹. This initial growth boost kept treated plants larger than untreated plants for up to six weeks, but at harvest there was no significant difference between control plants and treated plants. Possible effects of glyphosate hormesis on the competitive ability of spray drift affected plants are discussed.     

Adjusted blank correction method for UV–vis spectroscopic analysis of PTIO-coated filters used in nitrogen oxide passive samplers

Passive sampling devices are popular in applications which do not require the monitoring of hourly concentrations. Nitrogen oxides are often collected using filters coated with 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (PTIO). The filter extract can then be analyzed using flow injection analysis ion chromatography fitted with a copper/cadmium reduction column or UV–vis spectroscopy. When the latter is used to measure low concentrations of nitrogen oxides, absorbance by PTIO at the analytical wavelength of 545 nm contributes significantly. PTIO concentration on the filter also shows variation with filter storage and exposure time not accounted for in a single point blank subtraction at the analytical wavelength. A method is presented that uses a scaling factor to account for variations in concentration of PTIO on the field blank and provides a more accurate method for determining and correcting for the PTIO contribution to absorption when measuring ambient nitrogen oxide concentrations.     

Antimicrobial activity of metal oxide nanoparticles supported onto natural clinoptilolite

The antimicrobial activity of Cu₂O, ZnO and NiO nanoparticles supported onto natural clinoptilolite was investigated in the secondary effluent under dark conditions. After 24 h of contact the Cu₂O and ZnO nanoparticles reduced the numbers of viable bacterial cells of Escherichia coli and Staphylococcus aureus in pure culture for four to six orders of magnitude and showed consistent 100% of antibacterial activity against native E. coli after 1 h of contact during 48 exposures. The antibacterial activity of NiO nanoparticles was less efficient. The Cu₂O and NiO nanoparticles showed 100% of antiprotozoan activity against Paramecium caudatum and Euplotes affinis after 1 h of contact, while ZnO nanoparticles were less efficient. The morphology and crystallinity of the nanoparticles were not affected by microorganisms. The metal oxide nanoparticles could find a novel application in the disinfection of secondary effluent and removal of pathogenic microorganisms in the tertiary stage of wastewater treatment.     

Hydrological and geochemical factors affecting leachate composition in municipal solid waste incinerator bottom ash: Part I: The hydrology of Landfill Lostorf, Switzerland

The objective of the investigation of the municipal solid waste incinerator (MSWI) bottom ash landfill, Landfill Lostorf, was to determine the residence time of water in the landfill and the flow paths through the landfill. Over a period of 22 months, measurements of rainfall, landfill discharge and leachate electrical conductivity were recorded and tracer experiments made. Over the yearly period 1995, approximately 50% of the incident rainfall was measured in the discharge. An analysis of single rain events showed that in winter, 90–100% of rainfall was expressed in the landfill discharge, whereas in summer months, the value was between 9 and 40% depending on the intensity of the rain event. The response to rainfall was rapid. Within 30–100 h, approximately 50% of water discharged in response to a rain event had left the landfill. The discharge was less than 4 l/min for approximately 50% of the measurement periods. Qualitative tracer studies with fluorescein, pyranine and iodide clearly showed the existence of preferential flow paths. This was further substantiated by quantitative tracer studies of single rain events using / ratios and electrical conductivity measurements. The proportion of rainwater passing directly through the landfill was found to be between 20 and 80% in summer months and around 10% in winter months. The difference has been ascribed to the water content in the landfill. The average residence time of the water within the landfill has been estimated to be roughly 3 years and this water is the predominant component in the discharge over a yearly period.     

Adsorption characteristics of benzene on biosolid adsorbent and commercial activated carbons

This study selected biosolids from a petrochemical waste-water treatment plant as the raw material. The sludge was immersed in 0.5-5 M of zinc chloride (ZnCl2) solutions and pyrolyzed at different temperatures and times. Results indicated that the 1-M ZnCl2-immersed biosolids pyrolyzed at 500 degrees C for 30 min could be reused and were optimal biosolid adsorbents for benzene adsorption. Pore volume distribution analysis indicated that the mesopore contributed more than the macropore and micropore in the biosolid adsorbent. The benzene adsorption capacity of the biosolid adsorbent was 65 and 55% of the G206 (granular-activated carbon) and BPL (coal-based activated carbon; Calgon, Carbon Corp.) activated carbons, respectively. Data from the adsorption and desorption cycles indicated that the benzene adsorption capacity of the biosolid adsorbent was insignificantly reduced compared with the first-run capacity of the adsorbent; therefore, the biosolid adsorbent could be reused as a commercial adsorbent, although its production cost is high.     

Disentangling horizontal pay dispersion: Experimental evidence

Although horizontal pay dispersion has been explored extensively using cross‐sectional field methods, it has received little attention using the control available through experimental designs. Many of the questions relevant to pay dispersion research can be addressed by taking an individual‐level experimental approach because this allows for clean separation of pay policies and individual effects. In this paper, we hypothesize both the motivation‐based and affect‐based effects of pay dispersion policies and test our hypotheses with a sample of over 400 participants in a real‐pay, real‐effort experiment. Results of the experiment provide support that two pay dispersion‐related pay policies, performance‐based pay dispersion and allocation criteria, have unique effects. Whereas motivation and performance effects are direct, pay satisfaction and interest in continuing work effects are the result of interactions, incorporating the performance level of workers. In follow‐up analyses, we find evidence that the temporal nature of responses to pay dispersion should be incorporated into future studies of pay dispersion.     

Multi-elemental EDXRF mapping of polluted soil from former horticultural land

The distribution of major and trace elements was systematically investigated by use of energy dispersive X-ray fluorescence spectrometry (EDXRF) on a former horticultural soil. The purpose of the study was to combine mapping of soil element concentration levels with multivariate statistics for characterisation of soil metal pollution in relation to previous and present land use. A 1-ha study site was chosen from a former horticulture where a previous preliminary survey indicated increased concentration levels of toxic elements. The soil was sampled from the top 20 cm of the soil surface in a 10 x 10-m grid-like pattern covering the 1-ha study area. In addition, three soil profiles were studied. The elemental composition of the soil samples was investigated by EDXRF while the composition of aqueous soil extracts was determined by total reflection X-ray fluorescence spectrometry (TXRF). Based on mapping and multivariate statistically analysis of the data obtained by EDXRF, most elements were found in almost constant concentration levels in the top soil throughout the investigated site. However, the contents of the toxic elements Zn, Cu, As, and Pb were found to vary significantly within the area. Hence, the samples with high accumulations of As also contained relatively high amounts of Zn, Cu, and Pb, which indicates that toxic-element-containing pesticides have been applied to the soil surface in the area of the former green houses at the study site. The Pb/As mass ratio in the soil indicates that PbHAsO3 was the preferential lead arsenate used for pest management at the investigated site, while Cu as Bordeaux liquid (CuSO4) and Zn were applied to minimize the leaf damaging effect from the former compounds. Calculations indicated that As annually was applied to the soil in the former greenhouses in doses up to 4 kg As/ha while Pb had been annually applied in doses up to 12 kg Pb/ha. The enrichment of Zn, Cu, As and Pb was greatest in the top 20 cm of the soil and no anthropogenic enrichment of these elements occurred below a depth of 50 cm, indicating that the toxic elements are rather immobile in this soil. The results of this investigation suggest that EDXRF used in combination with multivariate statistics is a strong tool for multi-element mapping of elemental contents, sources and mobility in the terrestrial environment.     

Relationship between the riverine nitrate–nitrogen concentration and the land use in the Teshio River watershed, North Japan

The present research investigated the relationship between nitrate–nitrogen (NO₃–N) in river water and the land use/land cover (hereafter, land use) in the Teshio River watershed located in northern Hokkaido island to understand the effect of human activities such as agriculture, forestry, industry, and urbanization in the drainage basin on the river ecosystem quality and services. River water was sampled at nine points seasonally during a 2-year period and the nutrients concentration was measured. Land use profiles were estimated at two spatial scales, riparian and sub-catchment, for each sampling station. The spatial pattern of water quality in the Teshio River showed increased NO₃–N levels associated with agriculture and urban expansion, and forest reduction in the watershed. Land use at the riparian scale closely reflected that at the sub-catchment scale, which masked the unique riparian buffer effect on the river water condition. The increased agricultural and reduced forest area in the riparian zone, especially in the upper middle reach, could be a possible reason for a decline of ecosystem service for the provisioning of clean water and habitat for aquatic organisms. Measures towards sustainable and more nature-friendly agricultural management are necessary in the area to protect the Teshio River ecosystem and its ecosystem services.     

Fate of ah receptor agonists during biological treatment of an industrial sludge containing explosives and pharmaceutical residues

GOAL, SCOPE AND BACKGROUND: Sweden is meeting prohibition for deposition of organic waste from 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 higher degree. Two biological treatment alternatives are anaerobic digestion and composting. Different oxygen concentrations result in different microbial degradation pathways and, consequently, in a different quality of the digestion or composting residue, It is therefore necessary to study sludge treatment during different oxygen regimes in order to follow both degradation of compounds and change in toxicity. In this study, an industrial sludge containing explosives and pharmaceutical residues was treated with anaerobic digestion or composting, and the change in toxicity was studied. Nitroaromatic compounds, which are the main ingredients of both pharmaceutical and explosives, are well known to cause cytotoxicity and genotoxicity. However, little data are available concerning sludge with nitroaromatics and any associated dioxin-like activity. Therefore, we studied the sludge before and after the treatments in order to detect any changes in levels of Ah receptor (AhR) agonists using two bioassays for dioxin-like compounds. METHODS: An industrial sludge was treated with anaerobic digestion or composting in small reactors in a semi-continuous manner. The same volume as the feeding volume was taken out daily and stored at -20 degrees C. Sample preparation for the bioassays was done by extraction using organic solvents, followed by clean up with silica gel or sulphuric acid, yielding two fractions. The fractions were dissolved in DMSO and tested in the bioassays. The dioxin-like activity was measured using the DR-CALUX assay with transfected H4IIE rat hepatoma pGudluc cells and an EROD induction assay with RTL-W1 rainbow trout liver cells. RESULTS AND DISCUSSION: The bioassays showed that the sludge contained AhR agonists at levels of TCDD equivalents (TEQs) higher than other sludge types in Sweden. In addition, the TEQ values for the acid resistant fractions increased considerably after anaerobic digestion, resulting in an apparent formation of acid resistant TEQs in the anaerobic reactors. Similar results have been reported from studies of fermented household waste. There was a large difference in effects between the two bioassays, with higher TEQ levels in the RTL-W1 EROD assay than in the DR-CALUX assay. This is possibly due to a more rapid metabolism in rat hepatocytes than in trout hepatocytes or to differences in sensitivities for the AhR agonists in the sludge. It was also demonstrated by GC/FID analysis that the sludge contained high concentrations of nitroaromatics. It is suggested that nitroaromatic metabolites, such as aromatic amines and nitroanilines, are possible candidates for the observed bioassay effects. It was also found that the AhR agonists in the sludge samples were volatile. CONCLUSIONS: The sludge contained fairly high concentrations of volatile AhR agonists. The increase of acid resistant AhR agonist after anaerobic digestion warrants further investigations of the chemical and toxic properties of these compounds and of the mechanisms behind this observation. RECOMMENDATION AND OUTLOOK: This study has pointed out the benefits of using different types of mechanism-specific bioassays when evaluating the change in toxicity by sludge treatment, in which measurement of dioxin-like activity can be a valuable tool. In order to study the recalcitrant properties of the compounds in the sludge using the DR-CALUX assay, the exposure time can be varied between 6 and 24 hours. The properties of the acid-resistant AhR agonists formed in the anaerobic treatment have to be investigated in order to choose the most appropriate method for sludge management.