Pollutant concentration profile reconstruction using digital soft sensors for biodegradation and exposure assessment in the presence of model uncertainty

A new approach to the problem of environmental hazard assessment and monitoring for pollutant biodegradation reaction systems in the presence of uncertainty is proposed using soft sensor-based pollutant concentration dynamic profile reconstruction techniques. In particular, a robust reduced-order soft sensor is proposed that can be digitally implemented in the presence of inherent complexity and the inevitable model uncertainty. The proposed method explicitly incorporates all the available information associated with a process model characterized by varying degrees of uncertainty, as well as available sensor measurements of certain physicochemical quantities. Based on the above information, a reduced-order soft sensor is designed enabling the reliable reconstruction of pollutant concentration profiles in complex biodegradation systems that can not be always achieved due to physical and/or technical limitations associated with current sensor technology. The option of using the aforementioned approach to compute toxic load and persistence indexes on the basis of the reconstructed concentration profiles is also pursued. Finally, the performance of the proposed method is evaluated in two illustrative environmental hazard assessment case studies.     

Development of soil chemical and biological properties in the initial stages of post-mining deposition sites

The aim of this study was to assess the seasonal development of the physicochemical (pH, organic C, organic N, extractable P, Ca²⁺, Mg²⁺) and biological soil properties (microbial biomass, activities of urease, dehydrogenase and alkaline phosphatase) of the topsoil of mine deposition sites that differed based on the material used exclusively for their creation: (a) marlstones, (b) red-grey formations (RGF), and (c) fly ash (FA), during the first year after their creation. Our hypothesis was that all deposition sites, regardless the material they consist of, present equal opportunities for the establishment of spontaneous vegetation. All macronutrients concentrations (P, Ca²⁺, and Mg²⁺) remained constant with time and were found to be higher in the FA sites. Organic C, organic N, all enzyme activities, and microbial biomass were higher in the RGF and marl depositions, with marl sites presenting the highest values. All values of biological variables, with the exception of alkaline phosphatase, increased with time. The alkaline environment along with the slow improvement in soil biological properties of the FA sites seemed to present the most unfavorable conditions for spontaneous vegetation growth. On the contrary, the other two spoil materials presented significant improvement in the initial stages of soil formation in terms of soil functionality.     

Defining length-at-metamorphosis in fishes: a multi-character approach

The present study attempts to highlight the value of multi-character approaches for defining thresholds in fish ontogeny, like the onset of the juvenile period. We developed techniques to objectively define the transition from larval to juvenile development using morphometric as well as morphological characters and exemplify the multi-character approach on newly settled white sea-breams (Diplodus sargus sargus) collected from the eastern Mediterranean. The morphometric analysis was based on principles of multivariate allometry whereas the analysis of morphology, on assigning a suite of selected characters (here related to external morphology and osteological development) into larval, transforming and juvenile states. The size-at-change in multivariate allometric growth (L _m) is considered here to denote mean length-at-metamorphosis. An almost perfect match is demonstrated between L _m (‘multivariate morphometry’) and mean size-at-morphological change (‘multivariate morphology’) in white sea-bream.     

Fate of Irgarol 1051, diuron and their main metabolites in two UK marine systems after restrictions in antifouling paints

Two major antifouling biocides used worldwide, Irgarol 1051 and diuron, and their degradation products in Shoreham Harbour and Brighton Marina, UK were studied during 2003-2004. The highest concentrations of Irgarol 1051 were 136 and 102 ng L(-1) in water and 40 and 49 ng g(-1) dry weight in sediments for Shoreham Harbour and Brighton Marina, respectively. As the degradation product of Irgarol 1051, M1 was also widespread, with the highest concentration of 59 ng L(-1) in water and 23 ng g(-1) in sediments in Shoreham Harbour, and 37 ng L(-1) in water and 5.6 ng g(-1) in sediments in Brighton Marina. The target compounds showed enhanced concentrations during the boating season (May-July), when boats were being re-painted (January-February), and where the density of pleasure crafts was high. Overall, the concentration of Irgarol 1051 decreased significantly from late 2000 to early 2004, indicating the effectiveness of controlling its concentrations in the marine environment following restricted use. Diuron was only detected in 14% of water samples, and mostly absent from sediment samples.     

Evaluation of processes occurring in the bottom nepheloid layer (BNL) of an eastern Mediterranean area using 234Th/238U disequilibria

Particle-reactive radionuclide ²³⁴Th and its ratios with the conservative ²³⁸U were used to trace the marine processes occurring over short timescales in the bottom nepheloid layer (BNL) of seven stations in the Saronikos Gulf and the Elefsis Bay (Greece) during three seasons (summer 2008, autumn 2008 and winter 2009). Summer was considered as a steady season where low physical processes occur and stratification is well established, autumn as a commutative period and winter as period of extensive trawling and physical activities. The obtained ratio profiles showed excess of ²³⁴Th relative to ²³⁸U in the BNL of the sampling area during summer, caused by the dissolved fraction of ²³⁴Th. During autumn, the situation was different with large ²³⁴Th deficit throughout the water column leading to large export fluxes of particles from the water column. Finally, during winter the ratios showed that predominant phenomenon in the area was likely resuspension of bottom sediments. The resuspension signature was additionally evaluated by total suspended matter (TSM) inventories in the BNL. Despite the intense resuspension, small scavenging of dissolved ²³⁴Th was recorded in the BNL resulting in high residence times of dissolved ²³⁴Th. A 1 order of magnitude difference between dissolved and particulate ²³⁴Th residence times was observed indicating that scavenging from dissolved to particulate ²³⁴Th could be highly variable and, as a result, the Saronikos Gulf is a highly dynamic environment, in terms of temporal and spatial particle uptake and removal. Comparing these values to literature ones consistent results were obtained. The possibility of sediment resuspension in the BNL during winter was amplified by the bloom of phytoplankton resulting in even decreased residence times of particulate ²³⁴Th (average values). In contrast, the respective residence times of the dissolved fraction of ²³⁴Th in the BNL were higher showing a maximum in winter at the stations where resuspension concluded. Nevertheless, ²³⁴Th cycling in the area is not controlled by TSM, probably due to the presence of colloids, which could play an essential role in ²³⁴Th scavenging.     

Re-cycling of sugar-ash: a raw feed material for rotary kilns

Large amounts of sugar-ash, a material rich in calcium carbonate, are produced as a by-product in the Greek Sugar Industry. This work explores the possibility of re-cycling sugar-ash for use in the lime industry. A representative sample of sugar-ash from the Plati Imathias sugar plant was studied by PXRD, TG/DTG, calcination experiments at temperatures between 650 and 1150 degrees C and experiments to determine the quality of the quicklime produced at temperatures between 850 and 1150 degrees C following methods described in ASTM C110 standard. The sugar-ash was found to consist of 90 wt% calcium rich minerals (calcite and monohydrocalcite) and 10 wt% amorphous material. Traces of quartz were also detected. The quicklime of highest quality was produced at 950 degrees C. It is concluded that this "useless" material (sugar-ash) can be re-cycled for use in rotary kilns in the lime industry at calcination temperatures up to 950-1000 degrees C.     

A comparative chemometric study for water quality expertise of the Athenian water reservoirs

The aim of the present study is to compare the application of unsupervised and supervised pattern recognition techniques for the quality assessment and classification of the reservoirs used as the source for the domestic and industrial water supply of the city of Athens, Greece. A new optimization strategy for sampling, monitoring, and water management is proposed. During the period of October 2006 to April 2007, 89 samples were collected from the three water reservoirs (Iliki, Mornos, and Marathon), and 13 parameters (metals and metalloids) were analytically determined. Generally, all the elements were found to fluctuate at very low levels, especially for Mornos that comprises the main water reservoir of Athens. Iliki and Marathon showed relatively elevated values, compared to Mornos, but below the legislative limits. Multivariate unsupervised statistical techniques, such as factor analysis/principal components analysis, and cluster analysis and supervised ones, like discriminant analysis and classification trees, were applied to the data set, and their classification abilities were compared. All the chemometric techniques successfully revealed the critical variables and described the similarities and dissimilarities among the sampling points, emphasizing the individual characteristics in every sample and revealing the sources of elements in the region. New data from posterior samplings (November and December 2007) were used for the validation of the supervised techniques. Finally, water management strategies were proposed concerning the sampling points and representative parameters.     

Chemical composition and mass closure of ambient PM10 at urban sites

The chemical composition of PM10 was studied during summer and winter sampling campaigns conducted at two different urban sites in the city of Thessaloniki, Greece (urban-traffic, UT and urban-industrial, UI). PM10 samples were chemically analysed for minerals (Si, Al, Ca, Mg, Fe, Ti, K), trace elements (Cd, Cr, Cu, Mn, Pb, V, Zn, Te, Co, Ni, Se, Sr, As, and Sb), water-soluble ions (Cl^?, NO₃^?, SO₄^2?, Na⁺, K⁺, NH₄⁺, Ca²⁺, Mg²⁺) and carbonaceous compounds (OC, EC). Spatial variations of atmospheric concentrations showed significantly higher levels of minerals, some trace metals and TC at the UI site, while at the UT site significantly higher levels of elements like Cd, Ba, Sn, Sb and Te were observed. Crustal elements, excepting Ca at the UI site, did not exhibit significant seasonal variations at any site pointing to constant emissions throughout the year. In order to reconstruct the particle mass, the determined components were classified into six classes as follows: mineral matter (MIN), trace elements (TE), organic matter (OM), elemental carbon (EC), sea salt (SS) and secondary inorganic aerosol (SIA). Good correlations with slopes close to 1 were found between chemically determined and gravimetrically measured PM10 masses for both sites. According to the chemical mass closure obtained, the major components of PM10 at both sites were MIN (soil-derived compounds), followed by OM and SIA. The fraction unaccounted for by chemical analysis comprised on average 8% during winter and 15% during summer at the urban-industrial site, while at the urban-traffic site the percentages were 21.5% in winter and 4.8% in summer.     

Defining chemical status of a temporary Mediterranean River

Although the majority of rivers and streams in the Mediterranean area are temporary, no particular attention is being paid for such systems in the Water Framework Directive (WFD). A typical temporal Mediterranean river, draining an intensively cultivated basin, was assessed for its chemical status. Elevated concentrations of nitrates and salts in river water as well as nutrients and heavy metals in river sediments have been attributed to agricultural land uses and practices and point sources of organic pollution. A scheme for the classification of the river's chemical status (within the ecological quality classification procedure) was applied by combining pollution parameters in groups according to related pressures. In light of the temporal hydrological regime and anthropogenic impacts, sediment chemical quality elements were considered, in addition to hydrochemical ones. Despite the extensive agricultural activities in the basin, the majority of the sites examined showed a good quality and only three of them were classified as moderate. For the classification of the chemical quality of temporary water bodies, there is a need to develop ecologically relevant salinity and sediment quality standards.     

Sediment and Suspended Matter Lead Contamination in the Gulf of Kavala, Greece

Sediment and suspended particulate matter samples from 24 stations in the Gulf of Kavala have been examined for lead contamination. Grain size analysis and organic matter content were also performed. Total – anthropogenic sediment lead concentrations and enrichment factors at stations close to harbors and chemical industries were found higher (up to 209–135μg/g and 4.12 respectively), in relation to concentrations from the rest of the coastal zone. In the above areas, increased suspended particulate lead in the bottom of the water column was also recorded (up to 109μg/g). Total sediment lead concentrations composed of high natural Pb background increased with decreasing grain size, suggesting their association with the fine fractions of the sediments (31.1–66.0% mud presence) and the organic matter content (6–9% higher values). Overall, higher total lead concentrations in the sediments, determined by this work, appear to be significantly different from those reported for the Gulf of Kavala in previous studies and similar to those detected in other highly contaminated eastern Mediterranean coastal areas.