Sorption and mobility of pharmaceutical compounds in soil irrigated with reclaimed wastewater

Use of reclaimed wastewater for irrigation is an important route for the introduction of pharmaceutical compounds (PCs) into the environment. In this study, the mobility and sorption-desorption behavior of carbamazepine, naproxen and diclofenac were studied in soil layers sampled from a plot irrigated with secondary-treated wastewater (STWW). Carbamazepine and diclofenac were significantly retarded in the 0-5 cm soil sample rich in soil organic matter (SOM): carbamazepine was not affected by the water quality (freshwater versus STWW), whereas diclofenac exhibited a higher retardation factor (RF) in the freshwater system. Naproxen exhibited significantly lower RFs than diclofenac but with a similar trend - higher retardation in the freshwater versus STWW system. In the 5-15 cm soil sample containing low SOM, naproxen was highly mobile while carbamazepine and diclofenac were still retarded. In the 15-25 cm sample, all compounds exhibited their lowest RFs. Sorption data suggested that SOM governs the studied PCs' interactions with the soil samples. However, higher carbon-normalized sorption coefficients were measured for the PCs in the 15-25 cm sample, suggesting that both quantity and the physicochemical nature of SOM affect sorption interactions. While both naproxen and carbamazepine exhibited reversible sorption isotherms, diclofenac exhibited pronounced sorption-desorption hysteresis. This study suggests that carbamazepine and diclofenac can be classified as slow-mobile compounds in SOM-rich soil layers. When these compounds pass this layer and/or introduced into SOM-poor soils, their mobility increases significantly. This emphasizes the potential transport of PCs to groundwater in semiarid zones due to intensive irrigation with reclaimed wastewater in SOM-poor soils.     

Laboratory longitudinal diffusion tests: 2. Parameter estimation by inverse analysis

This study focuses on the verification of test interpretations for different state analyses of diffusion experiments. Part 1 of this study identified that steady, quasi-steady and equilibrium state analyses for the through- and in-diffusion tests with solution reservoirs are generally feasible where the tracer is not highly sorptive. In Part 2 we investigate parameter identifiability in transient-state analysis of reservoir concentration variation using a numerical approach. For increased generality, the analytical models, objective functions and Jacobian matrix necessary for inverse analysis of transient-state data are reformulated using unified dimensionless parameters. In these dimensionless forms, the number of unknown parameters is reduced and a single dimensionless parameter represents the sorption property. The dimensionless objective functions are evaluated for individual test methods and parameter identifiability is discussed in relation to the sorption property. The effects of multiple minima and measurement error on parameter identifiability are also investigated. The main findings are that inverse problems for inlet and outlet reservoir concentration analyses are generally unstable and well-posed, respectively. Where the tracer is sorptive, the inverse problem for the inlet reservoir concentration analysis may have multiple minima. When insufficient measurement data is collected, multiple solutions may result and this should be taken into consideration when inversely analyzing data including that of inlet reservoir concentration. Verification of test interpretation by cross-checking different state analyses is feasible where the tracer is not highly sorptive. In an actual experiment, test interpretation validity is demonstrated through consistency between theory and practice for different state analyses.     

Long-term geochemical evolution of the near field repository: insights from reactive transport modelling and experimental evidences

The KBS-3 underground nuclear waste repository concept designed by the Swedish Nuclear Fuel and Waste Management Co. (SKB) includes a bentonite buffer barrier surrounding the copper canisters and the iron insert where spent nuclear fuel will be placed. Bentonite is also part of the backfill material used to seal the access and deposition tunnels of the repository. The bentonite barrier has three main safety functions: to ensure the physical stability of the canister, to retard the intrusion of groundwater to the canisters, and in case of canister failure, to retard the migration of radionuclides to the geosphere. Laboratory experiments (< 10 years long) have provided evidence of the control exerted by accessory minerals and clay surfaces on the pore water chemistry. The evolution of the pore water chemistry will be a primordial factor on the long-term stability of the bentonite barrier, which is a key issue in the safety assessments of the KBS-3 concept.In this work we aim to study the long-term geochemical evolution of bentonite and its pore water in the evolving geochemical environment due to climate change. In order to do this, reactive transport simulations are used to predict the interaction between groundwater and bentonite which is simulated following two different pathways: (1) groundwater flow through the backfill in the deposition tunnels, eventually reaching the top of the deposition hole, and (2) direct connection between groundwater and bentonite rings through fractures in the granite crosscutting the deposition hole. The influence of changes in climate has been tested using three different waters interacting with the bentonite: present-day groundwater, water derived from ice melting, and deep-seated brine. Two commercial bentonites have been considered as buffer material, MX-80 and Deponit CA-N, and one natural clay (Friedland type) for the backfill. They show differences in the composition of the exchangeable cations and in the accessory mineral content. Results from the simulations indicate that pore water chemistry is controlled by the equilibrium with the accessory minerals, especially carbonates. pH is buffered by precipitation/dissolution of calcite and dolomite, when present. The equilibrium of these minerals is deeply influenced by gypsum dissolution and cation exchange reactions in the smectite interlayer. If carbonate minerals are initially absent in bentonite, pH is then controlled by surface acidity reactions in the hydroxyl groups at the edge sites of the clay fraction, although its buffering capacity is not as strong as the equilibrium with carbonate minerals. The redox capacity of the bentonite pore water system is mainly controlled by Fe(II)-bearing minerals (pyrite and siderite). Changes in the groundwater composition lead to variations in the cation exchange occupancy, and dissolution–precipitation of carbonate minerals and gypsum. The most significant changes in the evolution of the system are predicted when ice-melting water, which is highly diluted and alkaline, enters into the system. In this case, the dissolution of carbonate minerals is enhanced, increasing pH in the bentonite pore water. Moreover, a rapid change in the population of exchange sites in the smectite is expected due to the replacement of Na for Ca.     

Removal of insoluble chloride from bottom ash for recycling

In order to recycle bottom ash and use it as raw material for cement production, the removal of insoluble chloride was investigated by testing various washing techniques. The present work is also focused on investigating the properties of insoluble chlorides and determining the conditions for dissolving these compounds in order to reduce the chlorine content to the required level, i.e., less than 0.1 wt%. Within this framework, the effect of washing with water and CO2 bubbling was investigated, because the main insoluble chloride found in bottom ash, i.e., Friedel's salt, can be dissolved by CO2. Then, in order to better understand the removal of Cl, Friedel's salt was artificially synthesized by hydration and then the effect of CO2 bubbling was investigated. If all chlorides in the ash are converted into Friedel's salt by hydration, all chlorides can then be dissolved by CO2 bubbling. In addition, the effect of pH on removing the remaining insoluble chlorides was investigated by washing the ash with sulfuric acid solution. It was found that the most effective technique to reduce the Cl content to less than 1000 ppm was washing with sulfuric acid solution, while keeping the pH value at less than 4. By using this method, Friedel's salt and other insoluble chlorides were dissolved.     

Application of MSWI fly ash on acid soil and its effect on the environment

This study evaluated the feasibility of using municipal solid waste incinerator (MSWI) fly ash as acid soil amendment. In particular, changes in soil physicochemical properties and the potential environmental problems caused by the application of MSWI fly ash were investigated. The results showed that application of MSWI fly ash to the acid soil could raise the soil pH. The contents of rapidly available P and K, and slowly available K in the amended soil had a linear relationship with the addition ratio of MSWI fly ash. An addition of less than 20% of MSWI could raise the soil respiratory intensity after incubation for 3-5 days. Application of MSWI fly ash to the soil increased its content of water soluble salts and heavy metals, which could cause phytotoxicity in the plants. Therefore, the addition of MSWI fly ash to the soil should not be excessive, and less than 5-10% is an advisable addition level depending on the acidity of the soil and the plants growing on it.     

Household waste disposal in Mekelle city, Northern Ethiopia

In many cities of developing countries, such as Mekelle (Ethiopia), waste management is poor and solid wastes are dumped along roadsides and into open areas, endangering health and attracting vermin. The effects of demographic factors, economic and social status, waste and environmental attributes on household solid waste disposal are investigated using data from household survey. Household level data are then analyzed using multinomial logit estimation to determine the factors that affect household waste disposal decision making. Results show that demographic features such as age, education and household size have an insignificant impact over the choice of alternative waste disposal means, whereas the supply of waste facilities significantly affects waste disposal choice. Inadequate supply of waste containers and longer distance to these containers increase the probability of waste dumping in open areas and roadsides relative to the use of communal containers. Higher household income decreases the probability of using open areas and roadsides as waste destinations relative to communal containers. Measures to make the process of waste disposal less costly and ensuring well functioning institutional waste management would improve proper waste disposal.     

Effects of pesticides used in agriculture on the development of precocious puberty

The present study aims to evaluate the effects of pesticides on premature breast development. Forty-five girls (group 1) with premature breast development living in the Menderes region, where greenhouse cultivation is the main income, 16 girls (group 2) living in Izmir city with early puberty, and 33 girls (group 3) who had no signs of puberty were included in the study. Endosulphan 1, endosulphan 2, endosulphan sulphate, methoxychlor, vinclozolin, 4,4-dichlorodiphenyldichlorethylene (DDE), 4,-dichlorodiphenyltrichloroethane (DDT), and 2,4-DDT were evaluated in the serum and adipose tissues of the groups by using a gas chromatography-mass spectrometry method. With the exception of 4,4'-DDE, the pesticides studied were undetectable in the serum and adipose tissue samples. The levels of basal luteinizing hormone (LH), stimulated LH, follicle-stimulating hormone, and the long axis of the uterus and both ovaries were significantly different in the girls who had premature thelarche and detectable 4,4'-DDE levels compared to the girls who had premature thelarche and undetectable 4,4'-DDE levels in serum and adipose tissues. The presence and levels of pesticides in serum and adipose tissues were not related to precocious puberty (PP). The mechanisms that lead to PP may also result in obesity, and obesity may be the underlying cause for PP in this group.     

Alteration of potential harmful elements levels in sediments and biota from the central Mediterranean Sea (Aeolian Archipelago) following an episode of intense volcanic activity

In this paper levels of four (Hg, Cd, Pb, As) potential harmful elements (PHE) were measured in three different environmental matrices (sediments, macroalgae and fishes) from the Aeolian Archipelago and control areas both after 1 and 10 months from a volcanic activity of particular relevance occurred at the end of October 2002. Results were analysed on a multivariate statistical basis with the aim to evaluate: (I) general levels of pollution and increase of PHE due to the event; (II) differences observed among tested matrices in the time of recovery after the occurrence of the critical event; (III) the biological enrichment of PHE along the trophic web produced by the geological event. Results evidenced that volcanic emissions could represent a local source of particular relevance able to determine great enrichments of considered PHE in sediments and biological species. After 10 months from the event, levels in sediments and macroalgae notably decreased, whereas fish species evidenced an increase, principally related to the bioaccumulation phenomena. On the basis of the biological enrichment factors (BEF), major enrichments were evidenced after 1 month whereas, after 10 months, were recorded values reliable to an incomplete recovery. Concerning Cd, the BEF higher levels reported for the species Serranus cabrilla was probably related both to the diet and to the specific detoxification rates of this species.     

Elemental composition of sediments in Lake Jinzai, Japan: Assessment of sources and pollution

Bottom sediments from Lake Jinzai in southwest Japan were analyzed to determine their chemical compositions and to assess the potential for ecological harm by comparison with sediment quality guidelines. The pollution status of lake sediments was evaluated by employing contamination factor (CF), pollution load index (PLI), and geoaccumulation index (I(geo)), focusing on a suite of elements in lakebed and core sediments. Elevated concentrations of As, Pb, Zn, Cu, TOC, N, and P were present in several layers of the upper core and other surface sediments. The elevated metal concentrations are likely related to the fine-grained nature of the sediments, reducing bottom conditions produced by abundant organic matter, and possibly minor non-point anthropogenic sources. Moreover, correlations between the concentrations of trace metals and organic carbon, nitrogen, phosphorus, and iron, suggest that these elements play a role in controlling abundances. Calculated CF, PLI, and I(geo) indicate that the sediments are strongly polluted with respect to As, moderately to strongly polluted with Zn, and moderately polluted with Pb and Cu. Metal concentrations exceed the New York State Department of Environmental Conservation (NYSDEC) lowest effect level and the Canadian Council of Ministers of the Environment (CCME) interim sediment quality guidelines that indicate moderate impact on aquatic organisms in the study area.