Ecorisk evaluation and treatability potential of soils contaminated with petroleum hydrocarbon-based fuels

We used a series of toxicity tests to monitor oil degradation in the Kuwaiti oil lakes. Three soils from different locations with a history of hydrocarbon contamination were treated in bench-scale microcosms with controlled nutrient amendments, moisture content, and temperature that had promoted mineralization of total hydrocarbon and oil and grease in a preliminary study. Two hundred days of bioremediation treatment lowered hydrocarbon concentration to below 2 and 5 mg g(-1) for soils A and B, respectively, while in soil C hydrocarbon concentration remained at 12 mg g(-1). Although 85% of the total petroleum hydrocarbons (TPHs) in soil A were reduced 50d after treatment, results of the seed germination and Microtox tests suggested an initial increase in toxicity, indicating that toxic intermediary metabolites may have formed during biodegradation. Also, the significant decrease of TPHs and corresponding high toxicity levels were noted in soil B 200d after bioremediation. Clearly, toxicity values, and not just hydrocarbon concentration, are a key factor in assessing the effectiveness of bioremediation techniques. Field chemistry data showed a significant reduction in hydrocarbon levels after the biological treatment. We concluded that the toxicity assessment of the contaminated soil with a battery of toxicity bioassays could provide meaningful information regarding a characterization procedure in ecological risk assessment.     

Sorption of native polyaromatic hydrocarbons (PAH) to black carbon and amended activated carbon in soil

Organic pollutants (e.g. polyaromatic hydrocarbons (PAH)) strongly sorb to carbonaceous sorbents such as black carbon and activated carbon (BC and AC, respectively). For a creosote-contaminated soil (Sigma15PAH 5500 mg kg(dry weight(dw))(-1)) and an urban soil with moderate PAH content (Sigma15PAH 38 mg kg(dw)(-1)), total organic carbon-water distribution coefficients (K(TOC)) were up to a factor of 100 above values for amorphous (humic) organic carbon obtained by a frequently used Linear-Free-Energy Relationship. This increase could be explained by inclusion of BC (urban soil) or oil (creosote-contaminated soil) into the sorption model. AC is a manufactured sorbent for organic pollutants with similar strong sorption properties as the combustion by-product BC. AC has the potential to be used for in situ remediation of contaminated soils and sediments. The addition of small amounts of powdered AC (2%) to the moderately contaminated urban soil reduced the freely dissolved aqueous concentration of native PAH in soil/water suspensions up to 99%. For granulated AC amended to the urban soil, the reduction in freely dissolved concentrations was not as strong (median 64%), especially for the heavier PAH. This is probably due to blockage of the pore system of granulated AC resulting in AC deactivation by soil components. For powdered and granulated AC amended to the heavily contaminated creosote soil, median reductions were 63% and 4%, respectively, probably due to saturation of AC sorption sites by the high PAH concentrations and/or blockage of sorption sites and pores by oil.     

Dioxins in adipose tissue of women in Southern Spain

Seventeen polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were quantified in adipose tissue samples of non-occupationally exposed women living in Southern Spain. Geometric mean levels of sum of congeners and WHO(PCDD/F)-TEQ(2005) were 410 and 17.9pgg(-1) fat, respectively. Among PCDDs, octachlorodibenzo-p-dioxin (OCDD) showed the highest concentration with a mean value of 265pgg(-1) fat, followed by 1,2,3,6,7,8-HxCDD (49.3pgg(-1) fat) and 1,2,3,4,6,7,8-HpCDD (45.2pgg(-1) fat). These three congeners were responsible for around 90% of the sum of all PCDD/F congeners in adipose tissue. The geometric mean 2,3,7,8-TCDD value was 1.87pgg(-1) fat. 2,3,4,7,8-PeCDF (8.43pgg(-1) fat) showed the highest concentration among the PCDFs, followed by 1,2,3,4,7,8-HxCDF (4.17pgg(-1) fat) and 1,2,3,6,7,8-HxCDF (3.28pgg(-1) fat), and these three congeners were responsible for 4% of the sum of all studied PCDD/F congeners in adipose tissue and 76% of the sum of ten PCDFs. 1,2,3,7,8,9-HxCDF was the only congener not quantified in any sample, while 1,2,3,4,7,8,9-HpCDF, 1,2,3,7,8-PeCDF, OCDF and 2,3,7,8-TCDF were found in 5, 16, 16 and 19 samples, respectively. All other congeners were quantifiable in all 20 samples. Congeners contributing most to the WHO(PCDD/F)-TEQ(2005) were 1,2,3,7,8-PeCDD (31.6%), 1,2,3,6,7,8-HxCDD (28.3%) and 2,3,4,7,8-PeCDF (14.6%). The body burden of log-transformed WHO(PCDD/F)-TEQ(2005) levels increased with age (B=0.02; 95% CI=0.01, 0.03; p=0.02). Although these adipose tissue PCDD/F levels are similar to previously published findings in Spain and other European countries, further research is needed to determine trends in the exposure of women to these chemical residues.     

Non-Fickian dispersion in a single fracture

Solute transport in fractured rocks is of major interest in many applications, from the petroleum industry to ground water management. This work focuses on the dispersion process in a transparent replica of a real single fracture. The fracture exhibits strong changes in heterogeneity, with the first half very heterogeneous and the second half fairly homogeneous. Three models have been used to interpret the tracer experiments: the classical advection-dispersion equation (ADE), the continuous time random walk (CTRW), and the stratified model. The main goals were to test these models and to study possible correlations between fitting parameters and heterogeneities. As expected, the solution derived from the ADE equation appears to be unable to model long-time tailing behavior. On the other hand, the results confirm the CTRW robustness and the coefficient beta seems well correlated to heterogeneities. Finally, the stratified model is also able to describe non-Fickian dispersion. The parameters defined by this model are correlated to the heterogeneities of the fracture.     

A strategy for aromatic hydrocarbon bioremediation under anaerobic conditions and the impacts of ethanol: a microcosm study

Increased use of ethanol-blended gasoline (gasohol) and its potential release into the subsurface have spurred interest in studying the biodegradation of and interactions between ethanol and gasoline components such as benzene, toluene, ethylbenzene and xylene isomers (BTEX) in groundwater plumes. The preferred substrate status and the high biological oxygen demand (BOD) posed by ethanol and its biodegradation products suggests that anaerobic electron acceptors (EAs) will be required to support in situ bioremediation of BTEX. To develop a strategy for aromatic hydrocarbon bioremediation and to understand the impacts of ethanol on BTEX biodegradation under strictly anaerobic conditions, a microcosm experiment was conducted using pristine aquifer sand and groundwater obtained from Canadian Forces Base Borden, Canada. The initial electron accepter pool included nitrate, sulfate and/or ferric iron. The microcosms typically contained 400 g of sediment, 600 approximately 800 ml of groundwater, and with differing EAs added, and were run under anaerobic conditions. Ethanol was added to some at concentrations of 500 and 5000 mg/L. Trends for biodegradation of aromatic hydrocarbons for the Borden aquifer material were first developed in the absence of ethanol, The results showed that indigenous microorganisms could degrade all aromatic hydrocarbons (BTEX and trimethylbenzene isomers-TMB) under nitrate- and ferric iron-combined conditions, but not under sulfate-reducing conditions. Toluene, ethylbenzene and m/p-xylene were biodegraded under denitrifying conditions. However, the persistence of benzene indicated that enhancing denitrification alone was insufficient. Both benzene and o-xylene biodegraded significantly under iron-reducing conditions, but only after denitrification had removed other aromatics. For the trimethylbenzene isomers, 1,3,5-TMB biodegradation was found under denitrifying and then iron-reducing conditions. Biodegradation of 1,2,3-TMB or 1,2,4-TMB was slower under iron-reducing conditions. This study suggests that addition of excess ferric iron combined with limited nitrate has promise for in situ bioremediation of BTEX and TMB in the Borden aquifer and possibly for other sites contaminated by hydrocarbons. This study is the first to report 1,2,3-TMB biodegradation under strictly anaerobic condition. With the addition of 500 mg/L ethanol but without EA addition, ethanol and its main intermediate, acetate, were quickly biodegraded within 41 d with methane as a major product. Ethanol initially present at 5000 mg/L without EA addition declined slowly with the persistence of unidentified volatile fatty acids, likely propionate and butyrate, but less methane. In contrast, all ethanol disappeared with repeated additions of either nitrate or ferric iron, but acetate and unidentified intermediates persisted under iron-enhanced conditions. With the addition of 500 mg/L ethanol and nitrate, only minor toluene biodegradation was observed under denitrifying conditions and only after ethanol and acetate were utilized. The higher ethanol concentration (5000 mg/L) essentially shut down BTEX biodegradation likely due to high EA demand provided by ethanol and its intermediates. The negative findings for anaerobic BTEX biodegradation in the presence of ethanol and/or its biodegradation products are in contrast to recent research reported by Da Silva et al. [Da Silva, M.L.B., Ruiz-Aguilar, G.M.L., Alvarez, P.J.J., 2005. Enhanced anaerobic biodegradation of BTEX-ethanol mixtures in aquifer columns amended with sulfate, chelated ferric iron or nitrate. Biodegradation. 16, 105-114]. Our results suggest that the apparent conservation of high residual labile carbon as biodegradation products such as acetate makes natural attenuation of aromatics less effective, and makes subsequent addition of EAs to promote in situ BTEX biodegradation problematic.     

Simultaneous treatment of PVC and oyster-shell wastes by mechanochemical means

This work presents a new process for dechlorinating poly-vinyl chloride (PVC) by the use of oyster-shell waste. The process consists of milling of PVC waste with oyster-shell waste, followed by washing the milled sample with water. The milling of PVC and oyster-shell mixture results in size reduction and rupture in bonds, leading to mechanically induced reactions between the two to form CaCl2 and hydrocarbon with C=C bonds. Washing the milled mixtures with water at room temperature allows complete removal of chlorine from the milled sample. More than 95% of chlorine in PVC was removed when 2h grinding is conducted for the mixture. The present process could offer a potential route to the handling and disposal of oyster-shell and PVC wastes.     

Architects' perspectives on construction waste reduction by design

The construction, demolition and excavation waste arising in England was estimated at 91 million tonnes in 2003. The current thinking on construction waste minimisation is heavily focussed on several issues relating to physical construction waste and recycling guides. Indeed, much had been published on ways to improve on-site waste management and recycling activities but very few attempts made to address the effect of design practices on waste generation. However, there is a consensus in the literature that the architect has a decisive role to play in helping to reduce waste by focussing on designing out waste. This paper examines previous studies on architects' approach towards construction waste minimisation; and by means of a postal questionnaire, investigates: the origins of waste; waste minimisation design practices in the UK; and responsibilities and barriers within the UK architectural profession. The findings reveal that waste management is not a priority in the design process. Additionally, the architects seemed to take the view that waste is mainly produced during site operations and rarely generated during the design stages; however, about one-third of construction waste could essentially arise from design decisions. Results also indicate that a number of constraints, namely: lack of interest from clients; attitudes towards waste minimisation; and training all act as disincentives to a proactive and sustainable implementation of waste reduction strategies during the design process.     

Improvements of nano-SiO2 on sludge/fly ash mortar

Sewage sludge ash has been widely applied to cementitious materials. In this study, in order to determine effects of nano-SiO(2) additives on properties of sludge/fly ash mortar, different amounts of nano-SiO(2) were added to sludge/fly ash mortar specimens to investigate their physical properties and micro-structures. A water-binding ratio of 0.7 was assigned to the mix. Substitution amounts of 0%, 10%, 20%, and 30% of sludge/fly ash (1:1 ratio) were proposed. Moreover, 0%, 1%, 2%, and 3% of nano-SiO(2) was added to the mix. Tests, including SEM and compressive strength, were carried out on mortar specimens cured at 3, 7, and 28 days. Results showed that sludge/fly ash can make the crystals of cement hydration product finer. Moreover, crystals increased after nano-SiO(2) was added. Hence, nano-SiO(2) can improve the effects of sludge/fly ash on the hydration of mortar. Further, due to the low pozzolanic reaction active index of sludge ash, early compressive strengths of sludge/fly ash mortar were decreased. Yet, nano-SiO(2) could help produce hydration crystals, which implies that the addition of nano-SiO(2) to mortar can improve the influence of sludge/fly ash on the development of the early strength of the mortar.     

Composting olive mill pomace and other residues from rural southeastern Spain

The costly disposal of the semisolid residual pomace generated in the two phase extraction used in modern olive mills is causing serious problems to the small oil producers of rural southeastern Spain. Composting may be a viable alternative since complementary residues are usually available in these areas to prepare an adequate starting mixture. In this work, four different combinations of residues (pomace+rabbit manure, pomace+sheep manure, pomace+rabbit manure+rice straw, pomace+rabbit manure+almond shells) were composted in 3 ton piles aerated by turnings, using technology available to any small community of oil producers. During the four long processes (9-10 months), a steady decrease of organic matter and increases in the concentrations of nutrient and humic substances were observed, together with large increases in pH and salinity which may reduce the agronomic value of the final products.