Lead accumulation in different Chinese cabbage cultivars and screening for pollution-safe cultivars

Recently, the concept of pollution-safe cultivars (PSCs) was proposed to minimize the influx of pollutants to the human food chain. Variations in lead (Pb) uptake and translocation among Chinese cabbage (Brassica pekinensis L.) cultivars were investigated in a pot-culture experiment and a field-culture experiment to screen out Pb-PSCs for food safety. The results of the pot-culture experiment showed that shoot Pb concentrations under two Pb treatments (500 and 1500 mg kg^?1) varied significantly (p < 0.05) between cultivars, with average values of 3.01 and 6.87 mg kg^?1, respectively. Enrichment factors (EFs) and translocation factors (TFs) in cultivars were less than 0.50 and varied significantly (p < 0.05) between cultivars. Shoot Pb concentrations in 12 cultivars under treatment T₁ (500 mg kg^?1) were lower than 2.0 mg kg^?1. The field-culture experiment further confirmed Qiuao, Shiboqiukang and Fuxing 80 as Pb-PSCs, which were suitable to be cultivated in low-Pb (<382.25 mg kg^?1) contaminated soils and harmless to human health as foods.     

Nitrogen critical loads and management alternatives for N-impacted ecosystems in California

Empirical critical loads for N deposition effects and maps showing areas projected to be in exceedance of the critical load (CL) are given for seven major vegetation types in California. Thirty-five percent of the land area for these vegetation types (99,639 km²) is estimated to be in excess of the N CL. Low CL values (3–8 kg N ha^?1 yr^?1) were determined for mixed conifer forests, chaparral and oak woodlands due to highly N-sensitive biota (lichens) and N-poor or low biomass vegetation in the case of coastal sage scrub (CSS), annual grassland, and desert scrub vegetation. At these N deposition critical loads the latter three ecosystem types are at risk of major vegetation type change because N enrichment favors invasion by exotic annual grasses. Fifty-four and forty-four percent of the area for CSS and grasslands are in exceedance of the CL for invasive grasses, while 53 and 41% of the chaparral and oak woodland areas are in exceedance of the CL for impacts on epiphytic lichen communities. Approximately 30% of the desert (based on invasive grasses and increased fire risk) and mixed conifer forest (based on lichen community changes) areas are in exceedance of the CL. These ecosystems are generally located further from emissions sources than many grasslands or CSS areas. By comparison, only 3–15% of the forested and chaparral land areas are estimated to be in exceedance of the NO₃^? leaching CL. The CL for incipient N saturation in mixed conifer forest catchments was 17 kg N ha^?1 yr^?1. In 10% of the CL exceedance areas for all seven vegetation types combined, the CL is exceeded by at least 10 kg N ha^?1 yr^?1, and in 27% of the exceedance areas the CL is exceeded by at least 5 kg N ha^?1 yr^?1. Management strategies for mitigating the effects of excess N are based on reducing N emissions and reducing site N capital through approaches such as biomass removal and prescribed fire or control of invasive grasses by mowing, selective herbicides, weeding or domestic animal grazing. Ultimately, decreases in N deposition are needed for long-term ecosystem protection and sustainability, and this is the only strategy that will protect epiphytic lichen communities.     

Transfer characteristics of cobalt from soil to crops in the suburban areas of Fujian Province,southeast China

The bioavailability of cobalt and its transfer from soil to vegetables and rice were investigated. Among 312 soils collected from vegetable and paddy fields in the suburban areas of some major cities of Fujian Province, southeast China, total soil Co ranged from 3.5 to 21.7 mg kg^?1, indicating a slight accumulation compared with the background value of the province. DTPA extracted 0.1–8.5% of soil total Co. Total and DTPA-extractable Co correlated with soil pH, CEC, free Fe, total Mn, clay and silt content more significantly in paddy soils than in the soils from vegetable fields. The average Co concentrations in the edible parts of vegetables and rice were 15.4 μg kg^?1 and 15.5 μg kg^?1, respectively. The transfer factor (the ratio of plant Co to soil DTPA-extractable Co, TF_DTPA) ranged from 0.003 to 0.126 with a median of 0.049. The TF_DTPA decreased in the order of leafy vegetables > fruit vegetables > root vegetables > rice. The TF_DTPA of all crops decreased with increasing DTPA-extractable Co. Increase in pH, CEC, organic matter, clay, silt, free iron and total Mn limited the soil-to-plant transfer of Co to varying degrees. The transfer of Co from the soils to the edible parts of the crops was lower than that of Zn, Cu and Cd, but higher than that of Pb in the same areas. The concentrations of Co in rice and vegetables in the study areas were considered to be safe for the local residents because of the slight anthropogenic input and the low transfer potential to the edible parts of Co from the soils.     

Subsoil TPH contamination in two oil pipeline pumping stations and one pipeline right-of-way in north Mexico

This investigation deals with the characterization carried out in zones around two pipeline pumping stations and one pipeline right-of-way in the north of Mexico. In particular those areas where contamination was evaluated: (a) south area of the separation ditch in the Avalos station, (b) the area between the separation ditch at the Avalos station, (c) km 194 + 420 of the Moctuzma station, and (d) km 286 + 900 in the Candelaria station. Results of this investigation showed that only four samples showed TPH values higher than the Mexican limit for 2004: AVA 1B, with 21,191 mg kg^?1; AVA 1C, with 9348 mg kg^?1; AVA 2B, with 13,970 mg kg^?1; and MOC 2A, with 4108 mg kg^?1.None of the sampled points showed the presence of PAHs at values higher than those found in the Mexican or American legislations. PAH were detected in the range of 0.0004 and 13.05 mg kg^?1.It is suggested to implement surfactant soil washing as a remediation technique for the approximately 600 m³ that need to be treated.     

Effects of liming on soil properties and plant performance of temperate mountainous grasslands

The application of lime or liming materials to acid-soil grasslands might help mitigate soil acidity, a major constraint to forage productivity in many temperate mountainous grasslands. Nowadays, in these mountainous grasslands, it is essential to promote agricultural practices to increase forage yield and nutritive value while preserving biodiversity and agroecosystem functioning. Two different field experiments were conducted in the Gorbeia Natural Park, northern Spain: (i) one in a calcareous mountainous grassland (Arraba) and (ii) the other in a siliceous mountainous grassland (Kurtzegan) to study the effects of a single application of two liming products, i.e. 2429 kg lime (164.3% CaCO₃) ha^?1 and 4734 kg calcareous sand (84.3% CaCO₃) ha^?1, applied one month before the beginning of the sheep grazing season (May–October), on soil chemical (pH, organic C, total N, C/N ratio, %Al saturation, Olsen P, exchangeable K⁺ and Ca²⁺) and biological parameters (dehydrogenase, β-glucosidase, urease, acid phosphatase and arylsulphatase activity) as well as on botanical diversity (graminoids, forbs, shrubs) and forage yield and nutritive value (crude protein, modified acid detergent fibre, digestibility). Untreated control plots were also included in the experiment. Soil sampling was carried out at the end of the sheep grazing season (6 months after liming treatment), while botanical composition was determined one year after treatments application. Although no increase in soil pH was observed in Arraba, liming significantly increased dehydrogenase activity (an indicator of soil microbial activity) by 30.4 and 86.7% at Arraba and Kurtzegan site, respectively. Liming treatments significantly improved forage yield and nutritive value in Arraba but not in Kurtzegan. Furthermore, no differences in soil biological quality, evaluated using the “treated-soil quality index” as proposed in this work, were observed between treated and untreated soils, and between the two different lime treatments (lime, calcareous sand). It was concluded that, in acid-soil temperate mountainous grasslands, moderate liming treatments have no negative short-term effects either on soil quality or botanical composition, while resulting in improvements in forage yield and nutritive value under some conditions.     

The impact of urbanization on tropical mangroves (Fortaleza,Brazil): Evidence from PAH distribution in sediments

This investigation represents the first environmental diagnosis of the distribution and sources of polycyclic aromatic hydrocarbons (PAHs) in sediments from a tropical mangrove in Fortaleza, northeastern Brazil. Sediment cores from six sampling stations in the Cocó and Ceará Rivers were retrieved in June-July 2006 to determine 17 priority PAHs. The total PAH concentrations (Σ_PAHs) ranged from 3.04 to 2234.76 μg kg^?1(Cocó River) and from 3.34 to 1859.21 μg kg^?1 (Ceará River). These levels are higher than those of other cities with more industrial development. PAH concentrations did not reach probable effect levels (PELs). However, from 4.5 to 87.5% of individual PAH concentrations can occasionally cause adverse biological effects for aquatic organisms. The PAH molecular ratios indicate that the PAHs in the sediment core were derived mainly from petroleum, wood, and charcoal combustion (pyrogenic source), and that atmospheric deposition and urban runoff may serve as important pathways for PAH input to the sediment. Clearly, the Σ_PAHs in sediments collected in the Cocó and Ceará Rivers indicate that ongoing pollution is more severe than past pollution.     

Analytical solution for Joule–Thomson cooling during CO2 geo-sequestration in depleted oil and gas reservoirs

Mathematical tools are needed to screen out sites where Joule–Thomson cooling is a prohibitive factor for CO₂ geo-sequestration and to design approaches to mitigate the effect. In this paper, a simple analytical solution is developed by invoking steady-state flow and constant thermophysical properties. The analytical solution allows fast evaluation of spatiotemporal temperature fields, resulting from constant-rate CO₂ injection. The applicability of the analytical solution is demonstrated by comparison with non-isothermal simulation results from the reservoir simulator TOUGH2. Analysis confirms that for an injection rate of 3 kg s^?1 (0.1 MT yr^?1) into moderately warm (>40 °C) and permeable formations (>10^?14 m² (10 mD)), JTC is unlikely to be a problem for initial reservoir pressures as low as 2 MPa (290 psi).     

Energy balances,greenhouse gas emissions and economics of biochar production from palm oil empty fruit bunches

This paper presents results from a gate-to-gate analysis of the energy balance, greenhouse gas (GHG) emissions and economic efficiency of biochar production from palm oil empty fruit bunches (EFB). The analysis is based on data obtained from EFB combustion in a slow pyrolysis plant in Selangor, Malaysia. The outputs of the slow pyrolysis plant are biochar, syngas, bio-oil and water vapor. The net energy yield of the biochar produced in the Selangor plant is 11.47 MJ kg⁻¹ EFB. The energy content of the biochar produced is higher than the energy required for producing the biochar, i.e. the energy balance of biochar production is positive. The combustion of EFB using diesel fuel has the largest energy demand of 2.31 MJ kg⁻¹ EFB in the pyrolysis process. Comparatively smaller amounts of energy are required as electricity (0.39 MJ kg⁻¹ EFB) and for transportation of biochar to the warehouse and the field (0.13 MJ kg⁻¹ EFB). The net greenhouse gas emissions of the studied biochar production account for 0.046 kg CO₂-equiv. kg⁻¹ EFB yr⁻¹ without considering fertilizer substitution effects and carbon accumulation from biochar in the soil. The studied biochar production is profitable where biochar can be sold for at least 533 US-$ t⁻¹. Potential measures for improvement are discussed, including higher productivity of biochar production, reduced energy consumption and efficient use of the byproducts from the slow pyrolysis.     

The Austrian P budget as a basis for resource optimization

Phosphorus (P) is a finite and non-substitutable resource that is essential to sustaining high levels of agricultural productivity but is also responsible for environmental problems, e.g., eutrophication. Based on the methodology of Material Flow Analysis, this study attempts to quantify all relevant flows and stocks of phosphorus (P) in Austria, with a special focus on waste and wastewater management. The system is modeled with the software STAN, which considers data uncertainty and applies data reconciliation and error propagation. The main novelty of this work lies in the high level of detail at which flows and stocks have been quantified to achieve a deeper understanding of the system and to provide a sound basis for the evaluation of various management options. The budget confirms on the one hand the dependence of mineral P fertilizer application (2 kg cap⁻¹ yr⁻¹), but it highlights on the other hand considerable unexploited potential for improvement. For example, municipal sewage sludge (0.75 kg cap⁻¹ yr⁻¹) and meat and bone meal (0.65 kg cap⁻¹ yr⁻¹) could potentially substitute 70% of the total applied mineral P fertilizers. However, recycling rates are low for several P flows (e.g., 27% of municipal sewage sludge; 3% of meat and bone meal). Therefore, Austria is building up a remarkable P stock (2.1 kg P cap⁻¹ yr⁻¹), mainly due to accumulation in landfills (1.1 kg P cap⁻¹ yr⁻¹) and agricultural soils (0.48 kg P cap⁻¹ yr⁻¹).     

Effects of sandy desertified land rehabilitation on soil carbon sequestration and aggregation in an arid region in China

The rehabilitation of sandy desertified land in semi-arid and arid regions has a great potential to increase carbon sequestration and improve soil quality. Our objective was to investigate the changes in the soil carbon pool and soil properties of surface soil (0–15 cm) under different types of rehabilitation management. Our study was done in the short-term (7 years) and long-term (32 years) desertification control sites in a marginal oasis of northwest China. The different management treatments were: (1) untreated shifting sand land as control; (2) sand-fixing shrubs with straw checkerboards; (3) poplar (Populus gansuensis) shelter forest; and (4) irrigated cropland after leveling sand dune. The results showed that the rehabilitation of severe sandy desertified land resulted in significant increases in soil organic C (SOC), inorganic C, and total N concentrations, as well as enhanced soil aggregation. Over a 7-year period of revegetation and cultivation, SOC concentration in the recovered shrub land, forest land and irrigated cropland increased by 4.1, 14.6 and 11.9 times compared to the control site (shifting sand land), and increased by 11.2, 17.0 and 23.0 times over the 32-year recovery period. Total N, labile C (KMnO₄–oxidation C), C management index (CMI) and inorganic C (CaCO₃–C) showed a similar increasing trend as SOC. The increased soil C and N was positively related to the accumulation of fine particle fractions. The accumulation of silt and clay, soil C and CaCO₃ enhanced the formation of aggregates, which was beneficial to mitigate wind erosion. The percentage of >0.25 mm dry aggregates increased from 18.0% in the control site to 20.0–87.2% in the recovery sites, and the mean weight diameter (MWD) of water-stable aggregates significantly increased, with a range of 0.09–0.30 mm at the recovery sites. Long-term irrigation and fertilization led to a greater soil C and N accumulation in cropland than in shrub and forest lands. The amount of soil C sequestration reached up to 1.8–9.4 and 7.5–17.3 Mg ha^?1 at the 0–15 cm layer over a 7- and 32-year rehabilitation period compared to the control site, suggesting that desertification control has a great potential for sequestering soil C and improving soil quality in northwest China.     

Butyltin occurrence and risk assessment in the sediments of the Iberian Peninsula

The occurrence of butyltin (BT) compounds in more than 50 recent sediment samples of the Iberian Peninsula, collected in the harbours of the western Mediterranean Sea (Spain) and the North Atlantic Ocean (Portugal), including domestic and industrial sewage disposal sites, has been assessed. The highest levels of tributyltin (TBT) (7673 μg kg^?1 dry wt.) were detected in commercial harbours associated with inputs from large vessels. However, relatively high TBT values (about 2150 μg kg^?1 dry wt.) were also detected in fishing and recreational boating areas. Spanish marinas and harbours are more polluted in terms of TBT (5–7673 μg kg^?1 dry wt.) compared to those in Portugal (4–12 μg kg^?1 dry wt.). Generally, the Mediterranean sediments show a BT distribution characterized by the predominance of TBT over the degradation products dibutyl (DBT) and monobutyltin (MBT), indicating the presence of recent inputs, in contrast to the Portuguese coastal distribution. Calculation of butyltin degradation indexes (BDI) confirmed a different trend, depending on the area. Furthermore, a comparative study of the occurrence of BT in different sewage sludge disposal sites shows that domestic primary sewage sludge effluents can contribute to coastal BT pollution, but to a lesser extent when compared with harbours. Historical trends (1995–2003) for Barcelona harbour reveal that BT regulations on the use of TBT-based antifouling paints have not been fully effective. Finally, a comparison against the existing sediment quality guidelines (SQGs) indicated that acute toxic effects could only be expected for TBT in some Mediterranean harbours; conversely, in every North Atlantic Ocean station, a lesser environmental threat for the harbour benthic community is expected.     

Treatment and toxicity evaluation of methylene blue using electrochemical oxidation,fly ash adsorption and combined electrochemical oxidation-fly ash adsorption

Treatment of a basic dye, methylene blue, by electrochemical oxidation, fly ash adsorption, and combined electrochemical oxidation-fly ash adsorption was compared. Methylene blue at 100 mg L^?1 was used in this study. The toxicity was also monitored by the Vibrio fischeri light inhibition test.When electrochemical oxidation was used, 99% color and 84% COD were removed from the methylene blue solution in 20 min at a current density of 428 A m^?2, NaCl of 1000 mg L^?1, and pH₀ of 7. However, the decolorized solution showed high toxicity (100% light inhibition).For fly ash adsorption, a high dose of fly ash (>20,000 mg L^?1) was needed to remove methylene blue, and the Freundlich isotherm described the adsorption behavior well.In the combined electrochemical oxidation-fly ash adsorption treatment, the addition of 4000 mg L^?1 fly ash effectively reduced intermediate toxicity and decreased the COD of the electrochemical oxidation-treated methylene blue solution. The results indicated that the combined process effectively removed color, COD, and intermediate toxicity of the methylene blue solution.     

Storage and characterization of cotton gin waste for ethanol production

In 2002, about 17.1 million bales of cotton were ginned in the United States and the estimated cotton gin waste was 2.25 × 10⁹ kg. The disposal of cotton gin waste (CGW) is a significant problem in the cotton ginning industry, but CGW could be potentially used as feedstock for bioethanol. Freshly discharged CGW and stored CGW were characterized for storage stability and potential for ethanol production by determining their summative compositions. The bulk densities of the fresh wet and dry CGW were 210.2 ± 59.9 kg m⁻³ and 183.3 ± 52.2 kg m⁻³, respectively. After six months of storage the volume of piles A, B, and C decreased by 38.7%, 41.5%, and 33.3%, respectively, relative to the volume of the pile at the start of the storage. The ash content of the CGW was very high ranging from 10% to 21% and the acid-insoluble fraction was high (21–24%). The total carbohydrate content was very low and ranged from 34% to 49%. After three months storage, chemical compositional analysis showed the loss of total carbohydrates was minimal but after six months, the losses were as high as 25%. This loss of carbohydrates suggests that under open storage conditions, the feedstock must be processed within three months to reduce ethanol yield losses.     

In-depth analysis of aluminum flows in Austria as a basis to increase resource efficiency

Based on the method of material flow analysis (MFA), a static model of Austrian aluminum (Al) flows in 2010 was developed. Extensive data research on Al production, consumption, trade and waste management was conducted and resulted in a detailed model of national Al resources. Data uncertainty was considered in the model based on the application of a rigorous concept for data quality assessment. The model results indicated that the growth of the Austrian “in-use” Al stock amounts to 11 ± 3.1 kg yr⁻¹ cap⁻¹. The total “in-use” Al stock was determined using a bottom-up approach, which produced an estimate of 260 kg Al cap⁻¹. Approximately 7 ± 1 kg of Al yr⁻¹ cap⁻¹ of old scrap was generated in 2010, of which 20% was not recovered because of losses in waste management processes. Quantitatively, approximately 40% of the total scrap input to secondary Al production originated from net imports, highlighting the import dependency of Austrian Al refiners and remelters. Uncertainties in the calculation of recycling indicators for the Austrian Al system with high shares of foreign scrap trade were exemplarily illustrated for the old scrap ratio (OSR) in secondary Al production, resulting in a possible range of OSRs between 0 and 66%. Overall, the detailed MFA in this study provides a basis to identify resource potentials as well as resource losses in the national Al system, and it will serve as a starting point for a dynamic Al model to be developed in the future.     

Optimization of Fenton oxidation pre-treatment for B. thuringiensis – Based production of value added products from wastewater sludge

Fenton oxidation pretreatment was investigated for enhancement of biodegradability of wastewater sludge (WWS) which was subsequently used as substrate for the production of value- added products. The Response surface method with fractional factorial and central composite designs was applied to determine the effects of Fenton parameters on solubilization and biodegradability of sludge and the optimization of the Fenton process. Maximum solubilization and biodegradability were obtained as 70% and 74%, respectively at the optimal conditions: 0.01 ml H₂O₂/g SS, 150 [H₂O₂]₀/[Fe²⁺]₀, 25 g/L TS, at 25 °C and 60 min duration. Further, these optimal conditions were tested for the production of a value added product, Bacillus thuringiensis (Bt) which is being used as a biopesticide in the agriculture and forestry sector. It was observed that Bt growth using Fenton oxidized sludge as a substrate was improved with a maximum total cell count of 1.63 × 10⁹ CFU ml^?1 and 96% sporulation after 48 h of fermentation. The results were also tested against ultrasonication treatment and the total cell count was found to be 4.08 × 10⁸ CFU ml^?1 with a sporulation of 90%. Hence, classic Fenton oxidation was demonstrated to be a rather more promising chemical pre-treatment for Bt - based biopesticide production using WWS when compared to ultrasonication as a physical pre-treatment.     

Catalysts and inhibitors for oxidative degradation of monoethanolamine

MEA solutions were subjected to oxidative degradation at both low and high gas rates. Solutions were degraded with 100 mL/min of 98%O₂/2%CO₂ with mass transfer achieved by vortexing. Solutions were analyzed for degradation products by IC and HPLC. In a parallel apparatus 7.5 L/min of 15%O₂/2%CO₂ was sparged through solution, with additional mass transfer achieved by vortexing. A Fourier Transform Infrared (FTIR) analyzer collected continuous gas-phase data on volatile products.Hydroxyethyl-formamide (HEF) and hydroxyethylimidazole (HEI) are the major liquid-phase oxidation products. In the presence of Fe²⁺ and Cu²⁺, HEF, HEI, and MEA losses increase by a factor of 3 compared to Fe²⁺ alone. Cr³⁺ and Ni²⁺, two metals present in stainless steel alloys, resulted in MEA losses that are 55% greater. In terms of oxidative degradation potential (greatest to lowest): Cu²⁺ > Cr³⁺/Ni²⁺ > Fe²⁺ > V⁵⁺.Inhibitor A reduces the formation of known products by 90% when catalyzed by Fe²⁺ and Cu²⁺ and by 99% with Cr³⁺/Ni²⁺. Inhibitor B reduces product rates by 97% and MEA losses by 75%, while a 100:1 ratio of EDTA to Fe²⁺ completely inhibits oxidation.     

Effect of salinity on metal-complex dye biosorption by Rhizopus arrhizus

In this study the biosorption of Yellow RL, a metal-complex anionic dye, by dried Rhizopus arrhizus, a filamentous fungus, was investigated as a function of initial solution pH, initial dye concentration and initial salt (sodium chloride) concentration. The fungus exhibited the maximal dye uptake at pH 2 in the absence and in the presence of salt. Dye uptake increased with the dye concentration up to 1000 mg l^?1 and diminished considerably in the presence of increasing concentrations of salt up to 50 g l^?1. The fungus biosorbed 85.4 mg dye g^?1of dried biomass at 100 mg l^?1 initial dye concentration in the absence of salt. When 50 g l^?1 salt was added to the biosorption medium, this value dropped to 60.8 mg g^?1 resulting in 28.8% reduction in biosorption capacity. The Redlich–Peterson and Langmuir–Freundlich were the most suitable adsorption models for describing the biosorption equilibrium data of the dye both individually and in salt containing medium. The pseudo-second-order and saturation type kinetic models depicted the biosorption kinetics accurately for all cases studied. Equilibrium and kinetic constants varied with the level of salt were expressed as a function of salt concentration.     

Experimental assessment of brine and/or CO2 leakage through well cements at reservoir conditions

Two sets of experiments on typical Class G well cement were carried out in the laboratory to understand better the potential processes involved in well leakage in the presence of CO₂. In the first set, good-quality cement samples of permeability in the order of 0.1 μD (10^?19 m²) were subjected to 90 days of flow through with CO₂-saturated brine at conditions of pressure, temperature and water salinity characteristic of a typical geological sequestration zone. Cement permeability dropped rapidly at the beginning of the experiment and remained almost constant thereafter, most likely mainly as a result of CO₂ exsolution from the saturated brine due to the pressure drop along the flow path which led to multi-phase flow, relative-permeability effects and the observed reduction in permeability. These processes are identical to those which would occur in the field as well if the cement sheath in the wellbore annulus is of good quality. The second set of experiments, carried out also at in situ conditions and using ethane rather than CO₂ to eliminate any possible geochemical effects, assessed the effect of annular spaces between wellbore casing and cement, and of radial cracks in cement on the effective permeability of the casing-cement assemblage. The results show that, if both the cement and the bond are of good quality, the effective permeability of the assemblage is extremely low (in the order of 1 nD, or 10^?21 m²). The presence of an annular gap and/or cracks in the order of 0.01–0.3 mm in aperture leads to a significant increase in effective permeability, which reaches values in the range of 0.1–1 mD (10^?15 m²). The results of both sets of experiments suggest that good cement and good bonding with casing and the surrounding rock will likely constitute a good and reliable barrier to the upward flow of CO₂ and/or CO₂-saturated brine. The presence of mechanical defects such as gaps in bonding between the casing or the formation, or cracks in the cement annulus itself, leads to flow paths with significant effective permeability. This indicates that the external and internal interfaces of cements in wells would most probably constitute the main flow pathways for fluids leakage in wellbores, including both gaseous/supercritical phase CO₂ and CO₂-saturated brine.     

Experimental investigation of the CO2 sealing efficiency of caprocks

Using a combination of experimental (petrophysical and mineralogical) methods, the effects of high-pressure CO₂ exposure on fluid transport properties and mineralogical composition of two pelitic caprocks, a limestone and a clay-rich marl lithotype have been studied. Single and multiphase permeability tests, gas breakthrough and diffusion experiments were conducted under in situ p/T conditions on cylindrical plugs (28.5 mm diameter, 10–20 mm thickness).The capillary CO₂ sealing efficiency of the initially water-saturated sample plugs was found to decrease in repetitive gas breakthrough experiments on the same sample from 0.74 to 0.41 MPa for the limestone and from 0.64 to 0.43 MPa for the marl. Helium breakthrough experiments before and after the CO₂ tests showed a decrease in capillary threshold (snap-off) pressure from 1.81 to 0.62 MPa for the limestone.Repetitive CO₂ diffusion experiments on the marlstone revealed an increase in the effective diffusion coefficient from 7.8 × 10^?11 to 1.2 × 10^?10 m².Single-phase (water) permeability coefficients derived from steady-state permeability tests ranged between 7 and 56 nano-Darcy and showed a consistent increase after each CO₂ test cycle. Effective gas permeabilities were generally one order of magnitude lower than water permeabilities and exhibit the same trend. XRD measurements performed before and after exposure to CO₂ did not reveal any distinct change in the mineral composition for both samples. Similarly, no significant changes were observed in specific surface areas (determined by BET) and pore-size distributions (determined by mercury injection porosimetry). High-pressure CO₂ sorption experiments on powdered samples revealed significant CO₂ sorption capacities of 0.27 and 0.14 mmol/g for the marlstone and the limestone, respectively.The changes in transport parameters in the absence of detectable mineral alterations may be explained by carbonate dissolution and further precipitation along a pH profile across the sample plug which would not be subject to quantitative mineral alteration.