Effect of metals on the adsorption and extractability of 14C-phenanthrene in soils

The fate of polycyclic aromatic hydrocarbons (PAHs) in contaminated soils may be affected by several environmental factors including the presence of co-contaminants. This study was conducted in order to assess the effect of metals on (i) the adsorption of 14C-phenanthrene in soils and (ii) its extractability and ability to form non-extractable residues. The first objective was accomplished using batch adsorption experiments with an uncontaminated agricultural soil spiked with the metals Cd, Cu, Pb, and Zn. Adsorption of phenanthrene was significantly higher after the addition of the metals (Kf = 21.48 vs. 8.55) and the desorption less readily reversible when compared to the unspiked soil. The extractability of phenanthrene was assessed with incubation (4 months, laboratory conditions) and microlysimeter experiments (6 months, natural climatic conditions) on three soils spiked with metals. All the soils were labelled with 14C-phenanthrene. The amount of extractable phenanthrene residues was significantly higher when the metals had been added to the soils. Nevertheless, the quantity of non-extractable residues was non-significantly different between the spiked and unspiked soils. The mechanism leading to increased adsorption and extractability of phenanthrene in the presence of metals is still unknown. In perspective, it would be interesting to assess the bioavailability of PAHs in the presence of metals in further experiments.     

Use of flue gas desulphurisation (FGD) waste and rejected fly ash in waste stabilization/solidification systems

Stabilization/solidification (S/S) processes have been used as the final treatment step for hazardous wastes prior to land disposal. Fly ash is a by-product of coal-fired power generation; a significant proportion of this material is low-grade, reject material (rFA) that is unsuitable as a cement replacement due to its high carbon content and large particle size (>45 microm). Flue gas desulphurization (FGD) sludge is a by-product from the air pollution control systems used in coal-fired power plants. The objective of this work was to investigate the performance of S/S waste binder systems containing these two waste materials (rFA and FGD). Strength tests show that cement-based waste forms with rFA and FGD replacement were suitable for disposal in landfills. The addition of an appropriate quantity of Ca(OH)2 and FGD reduces the deleterious effect of heavy metals on strength development. Results of TCLP testing and the progressive TCLP test show that cement-rFA-Ca(OH)2 systems with a range of FGD additions can form an effective S/S binder. The Leachability Index indicates that cement-based waste forms with rFA replacement were effective in reducing the mobility of heavy metals.     

Assessing Secchi and photic zone depth in the Baltic Sea from satellite data

Long-term trends in the Secchi depth of the Baltic Sea have been interpreted in terms of eutrophication. The spectral attenuation coefficient Kd (490) can be estimated from remote sensing data. Given the empirical and theoretical relationships between diffuse attenuation and Secchi depth, it is therefore possible to estimate the trophic state from remote sensing data. This paper considers relationships among remotely sensed and in-water measured K (490), and Secchi depth data obtained during dedicated sea-truthing campaigns in the eastern Baltic Proper in 1999 (4) and in the western Baltic Proper/Himmerfj?rden area during 2001 and 2002. In-water measurements are used to establish the relationship between the PAR and the spectral attenuation coefficient in the Baltic Sea via regression analysis. The analysis showed that in the area of investigation Kd(490) is about 1.48 times higher than Kd (PAR). This relationship is then used to define the link between the photic zone depth and the remote sensing optical depth, Kd (490)-1. The results show that the depth of the euphotic zone is about 6.8 times Kd (490)-1. The regression analysis between Kd (PAR) and Secchi depth confirmed previous work that Kd (PAR) is about 1.7 of the inverse Secchi depth. Furthermore, an in-water algorithm between Secchi depth and Kd (490) is used to simulate a Secchi depth map of the Baltic Sea from SeaWiFS Kd(490) data. This map is verified against sea-truthing data. Kd (490) data derived from satellite is compared to in situ Kd (490), and the sources of error are discussed.     

Measuring acid volatile sulphide in floodplain lake sediments: effect of reaction time, sample size and aeration

For the routine measurement of acid volatile sulphide (AVS) in floodplain lake sediments, an earlier published diffusion method was adapted and optimised. We evaluated the effect of reaction time, sample weight and passive sample aeration on AVS recovery, and determined the method's reproducibility. The optimal reaction time was 4 h. Losses of AVS due to sample aeration did not occur within 15 min of sample-air contact. Relative standard deviation was <2.5% for known sulphide solutions, was between 10% and 15% for AVS concentrations in sediments and <12% for SEM concentrations in sediments, generally. Sediment samples with known SEM and AVS content were used to compare results of the developed method with the purge-and-trap method. There is a good agreement with the purge-and-trap method for SEM concentrations. AVS concentrations measured with the diffusion method are higher than with the purge-and-trap method. We conclude that the adapted diffusion method is well suited for the routine measurement of AVS concentrations in floodplain sediments.     

Sampling and analytical methodology development for the determination of primary and secondary low molecular weight amines in ambient air

In this project, a sampling device and an analytical method have been developed to simultaneously analyse the most frequently found low molecular weight amines, including aliphatic, aromatic and alcohol amines. These amines are diethanolamine, ethanolamine, methylamine, isopropylamine, morpholine, dimethylamine, and aniline. A sampling device was developed using a 37 mm cassette with glass fibre filters impregnated with sulfuric acid. Immediately after sampling, the filter was transferred to vials containing a solution of dansyl chloride. Dansyl chloride was used for derivatisation because it forms aromatic sulfonamides that are fluorescent and easy to protonate for MS detection. The effect of using an internal standard made with the dansylated derivative of 1-(2-methoxyphenyl)piperazine (MOPIP) on the uncertainty and efficiency of the method was also evaluated. This internal standard was spiked directly onto filters. The coupling of HPLC/ESI-MS was used for the simultaneous analysis of all the derivatives. This method showed detection limits of about 0.03 microg mL(-1) to 0.3 microg mL(-1) of amine with an average expanded uncertainty of 3% to 6% depending on the amine. The methodology recoveries are close to 100% for all the amines, and the overall estimated expanded uncertainties vary between 10% and 13% depending on the amine. This new strategy will be useful in evaluating workplace air since a unique sampling system will be used, independent of the amine to be quantified.     

Assessing the effectiveness of marine reserves on unsustainably harvested long-lived sessile invertebrates

Although the rapid recovery of fishes after establishment of a marine reserve is well known, much less is known about the response of long-lived, sessile, benthic organisms to establishment of such reserves. Since antiquity, Mediterranean red coral (Corallium rubrum) has been harvested intensively for use in jewelry, and its distribution is currently smaller than its historical size throughout the Mediterranean Sea. To assess whether establishment of marine reserves is associated with a change in the size and number of red coral colonies that historically were not harvested sustainably, we analyzed temporal changes in mean colony diameter and density from 1992 to 2005 within red coral populations at different study sites in the Medes Islands Marine Reserve (established in 1992) and in adjacent unprotected areas. Moreover, we compared colony size in the Medes Islands Marine Reserve, where recreational diving is allowed and poaching has been observed after reserve establishment, with colony size in three other marine protected areas (Banyuls, Carry-le-Rouet, and Scandola) with the enforced prohibition of fishing and diving. At the end of the study, the size of red coral colonies at all sampling sites in the Medes Islands was significantly smaller than predicted by growth models and smaller than those in marine protected areas without fishing and diving. The annual number of recreational dives and the percent change in the basal diameter of red coral colonies were negatively correlated, which suggests that abrasion by divers may increase the mortality rates of the largest red coral colonies within this reserve . Our study is the first quantitative assessment of a poaching event, which was detected during our monitoring in 2002, inside the marine reserve. Poaching was associated with a loss of approximately 60% of the biomass of red coral colonies.     

Antibiotic resistance patterns of Salmonella and Escherichia coli in the groundwater of Cyprus

In addition to diet-based vectors of disease, the contribution of water-borne zoonotic agents to gastrointestinal illnesses may be significant, but this has yet to be investigated for Cyprus. Our main objective was to evaluate antibiotic resistance patterns of Salmonella and Escherichia coli in groundwater samples collected at confined animal feeding operations. This is the first report on the occurrence of antibiotic-resistant Salmonella and E. coli strains in the groundwater of Cyprus. Most of Salmonella isolates belonged to the subgroup enterica, whereas none of the E. coli isolates expressed the verotoxin-encoding gene. Out of 27 isolated Salmonella strains, nearly half of them were resistant to at least one or more antibiotic, whereas the highest resistance was exhibited by sulphamethoxazole (85%), followed by streptomycin (39%), and tetracycline (31%). For the E. coli isolates, nearly a third of them showed resistance to at least one antibiotic, whereas the selection of antibiotic resistance was equal among sulphamethoxazole, tetracycline and streptomycin (20%). This study demonstrated that Salmonella and E. coli in groundwater could pose a public health risk via oral ingestion of contaminated water. Best management practices are needed for overexploited groundwater supplies of rural areas, minimizing human exposure to antibiotic-resistant pathogens.     

Effect of nitrogen deposition on China's terrestrial carbon uptake in the context of multifactor environmental changes

The amount of atmospheric nitrogen (N) deposited on the land surface has increased globally and by nearly five times in China from 1901 to 2005. Little is known about how elevated reactive N input has affected the carbon (C) sequestration capability of China's terrestrial ecosystems, largely due to the lack of reliable data on N deposition. Here we have used a newly developed data set of historical N deposition at a spatial resolution of 10 km x 10 km in combination with other gridded historical information on climate, atmospheric composition, land use, and land management practices to drive a process-based ecosystem model, the dynamic land ecosystem model (DLEM) for examining how increasing N deposition and its interactions with other environmental changes have affected C fluxes and storage in China's terrestrial ecosystems during 1901-2005. Our model simulations indicate that increased N deposition has resulted in a net C sink of 62 Tg C/yr (1 Tg = 1012 g) in China's terrestrial ecosystems, totaling up to 6.51 Pg C (1 Pg = 10(15) g) in the past 105 years. During the study period, the N-induced C sequestration can compensate for more than 25% of fossil-fuel CO2 emission from China. The largest C sink was found in southeast China, a region that experienced the most significant increase of N deposition in the period 1901-2005. However, the net primary productivity induced by per-unit N deposition (referred to as ecosystem N use efficiency, ENUE, in this paper) has leveled off or declined since the 1980s. This indicates that part of the deposited N may not be invested to stimulate plant growth, but instead leave the ecosystem by various pathways. Except shrubland and northwest/southwest China, signs of N saturation are apparent in the rest major biome types and regions, with ENUE peaking in the 1980s and leveling off or declining thereafter. Therefore, to minimize the excessive N pollution while keeping the N-stimulated C uptake in China's terrestrial ecosystems, optimized management practices should be taken to increase N use efficiency rather than to keep raising N input level in the near future.     

Predator-prey spatial game as a tool to understand the effects of protected areas on harvester-wildlife interactions

No-take reserves are sometimes implemented for sustainable population harvesting because they offer opportunities for animals to spatially avoid harvesters, whereas harvesters can benefit in return from the reserve spillover. Here, we used the framework of predator-prey spatial games to understand how protected areas shape spatial interactions between harvesters and target species and determine animal mortality. In these spatial games, the "predator" searches for "prey" and matches their habitat use, unless it meets spatial constraints offering the opportunity for prey to avoid the mortality source. However, such prey refuges could attract predators in the surroundings, which questions the potential benefits for prey. We located, in the Geneva Basin (France), hunting dogs and wild boar Sus scrofa L. during hunting seasons with global positioning systems and very-high-frequency collars. We quantified how the proximity of the reserve shaped the matching between both habitat uses using multivariate analyses and linked these patterns to animals' mortality with a Cox regression analysis. Results showed that habitat uses by both protagonists disassociated only when hunters were spatially constrained by the reserve. In response, hunters increased hunting efforts near the reserve boundary, which induced a higher risk exposure for animals settled over the reserve. The mortality of adult wild boar decreased near the reserve as the mismatch between both habitat uses increased. However the opposite pattern was determined for younger individuals that suffered from the high level of hunting close to the reserve. The predator-prey analogy was an accurate prediction of how the protected area modified spatial relationships between harvesters and target species. Prey-searching strategies adopted by hunters around reserves strongly impacted animal mortality and the efficiency of the protected area for this harvested species. Increasing reserve sizes and/or implementing buffer areas with harvesting limitations can dampen this edge effect and helps harvesters to benefit durably from source populations of reserves. Predator-prey spatial games therefore provide a powerful theoretical background for understanding wildlife-harvester spatial interactions and developing substantial application for sustainable harvesting.     

Testing hypotheses in evolutionary ecology with imperfect detection: capture-recapture structural equation modeling

Studying evolutionary mechanisms in natural populations often requires testing multifactorial scenarios of causality involving direct and indirect relationships among individual and environmental variables. It is also essential to account for the imperfect detection of individuals to provide unbiased demographic parameter estimates. To cope with these issues, we developed a new approach combining structural equation models with capture-recapture models (CR-SEM) that allows the investigation of competing hypotheses about individual and environmental variability observed in demographic parameters. We employ Markov chain Monte Carlo sampling in a Bayesian framework to (1) estimate model parameters, (2) implement a model selection procedure to evaluate competing hypotheses about causal mechanisms, and (3) assess the fit of models to data using posterior predictive checks. We illustrate the value of our approach using two case studies on wild bird populations. We first show that CR-SEM can be useful to quantify the action of selection on a set of phenotypic traits with an analysis of selection gradients on morphological traits in Common Blackbirds (Turdus merula). In a second case study on Blue Tits (Cyanistes caeruleus), we illustrate the use of CR-SEM to study evolutionary trade-offs in the wild, while accounting for varying environmental conditions.