Madejón, P; Murillo, J M; Marañón, T; Cabrera, F; Soriano, M A
The failure of a tailing pond dam at the Aznalcóllar pyrite mine (SW Spain) in April 1998 released a toxic spill affecting approximately 4300 ha along the Agrio and Guadiamar valleys. Two years later, we have studied yield and concentration of mineral nutrients and trace elements in sunflower plants grown in the spill-affected soil, and in an adjacent unaffected soil as comparison. The study has been carried out in plants at seedling (V4) and mature (R8) stages. Shoot and root biomass of sunflower seedlings was significantly smaller in the affected soil than in the unaffected soil, but there was no significant difference at the mature stage. Oil production was greater in the spill-affected plants. We have not detected any 'fertilising' effect caused by the acid waters of the spill on the main nutrient (N, P and Ca) acquisition, as documented in 1998 for sunflower plants flooded by the spill. Sunflower plants growing in the spill-affected soil reached adequate levels of nutrients. None of the trace elements measured-As, Cd, Cu, Pb and Tl-reached levels either phytotoxic or toxic for humans or animals in seeds and the above-ground part of the spill-affected plants. We evaluate the potential use of sunflower plants for phytoremediation. The potential for phytoextraction is very low; however, it may be used for soil conservation. The production of oil (usable for industrial purposes) may add some value to this crop.
Olías, Manuel; Moral, Francisco; Galván, Laura; Cerón, Juan Carlos
In 1998, the Agrio and Guadiamar rivers underwent an enormous environmental disaster caused by the rupture of the Aznalcóllar tailings dam and the release of 6 hm(3) of pyrite sludge and acidic water. Both rivers run over recent alluvial materials which form a small-sized aquifer which is however important because underground water feeds the flow of the rivers. This work analyzes the state of groundwater 10 years after the spill. Before the dam failure, this aquifer was already contaminated in the zone nearest to the mine, to which the impact of the spill was added. Contamination levels in the alluvial aquifer of the Agrio River have decreased remarkably. However, they are still important, with acidic pH values and high concentrations of toxic elements (maximum values of 16 mg/L of Zn and 15 mg/L of Al). There are also important levels of contamination in the Guadiamar alluvial area closest to the mine, as well as in specific zones located further south. The concentration of toxic elements is mainly controlled by pH. The evolution of contaminant levels show a sharp decrease after the first years following the spill, followed by a subsequent stabilization. It is necessary to take measures for the recovery of the aquifer because, otherwise, groundwater will continue contributing contaminants into the Agrio and Guadiamar rivers.
Vidal, M; López-Sánchez, J F; Sastre, J; Jiménez, G; Dagnac, T; Rubio, R; Rauret, G
The interaction of several trace elements (Cd, Zn, Cu, Pb, As, Bi, and Tl) was studied by leaching experiments in agricultural soils affected by the Aznalcóllar toxic spill. The spill led to contamination by acid waste waters and sludge deposition. The levels of contamination recorded after the sludge was removed from soils showed that highly contaminated areas remained. A comparison of soils directly affected by sludge deposition and acid waste waters with soils contaminated only by acid waste waters demonstrated that Zn/As and Cd/As ratios were good indicators of the two contributions to the contamination. Soil samples were characterised and grouped according to their texture and carbonate content. The response of elements to single extractions with CaCl2 0.01 mol l-1, CaCl2 1 mol l-1, CH3COOH 0.43 mol l-1, and EDTA 0.05 mol l-1 enabled us to estimate their mobility in the soils. Cd and Zn were found to be the most mobile elements. Cu showed an intermediate mobility, especially in an acidic medium. Pb, As, Bi and Tl were found to be non-mobile elements. A comparison of referent, low and highly contaminated samples showed that the presence of sludge had an effect on desorption yields, in part due to the short-term after the contamination. Calculations of a relative scale of long-term mobility, between soils and trace elements, provided further conclusions derived from the use of single extractions.
Cárdenas, Ana M.; Bujalance, José L.; Hidalgo, Juan M.
This study is part of the Follow up Restoration Program of animal communities that colonize the Guadiamar River Basin. In 1998, the area was affected by a release of toxic sludge after the retention walls of the Aznalcóllar Mines (southern Iberian Peninsula) broke. The main objective of this study was to assess the current state of the population of Tenebrionidae, one of the most representative groups of edaphic Coleoptera inhabiting the Guadiamar River Basin. This paper analyses the progress made by the darkling beetle community six years after the disaster occurred and the Restoration Program was implemented. The study is based on faunistic data from systematic sampling carried out for six years to monitor plots distributed across the damaged area. To make an overall assessment of the tenebrionid fauna in relation to adjacent areas qualitative and quantitative ecological indices were applied, and temporal follow up and biogeographical comparisons were also made. The results indicate that, on the whole, tenebrionid fauna was somewhat affected by the Aznalcóllar Mine spill, and that a greater loss of fauna was detected closer to the accident site. The analysis of the temporal population dynamic suggests that the most affected zones are undergoing a process of re-colonization. However, this process varies widely by species and has not yet reached the expected levels of a non-affected river basin in the southern Iberian Peninsula. PMID:21864152
Cárdenas, Ana M; Bujalance, José L; Hidalgo, Juan M
This study is part of the Follow up Restoration Program of animal communities that colonize the Guadiamar River Basin. In 1998, the area was affected by a release of toxic sludge after the retention walls of the Aznalcóllar Mines (southern Iberian Peninsula) broke. The main objective of this study was to assess the current state of the population of Tenebrionidae, one of the most representative groups of edaphic Coleoptera inhabiting the Guadiamar River Basin. This paper analyses the progress made by the darkling beetle community six years after the disaster occurred and the Restoration Program was implemented. The study is based on faunistic data from systematic sampling carried out for six years to monitor plots distributed across the damaged area. To make an overall assessment of the tenebrionid fauna in relation to adjacent areas qualitative and quantitative ecological indices were applied, and temporal follow up and biogeographical comparisons were also made. The results indicate that, on the whole, tenebrionid fauna was somewhat affected by the Aznalcóllar Mine spill, and that a greater loss of fauna was detected closer to the accident site. The analysis of the temporal population dynamic suggests that the most affected zones are undergoing a process of re-colonization. However, this process varies widely by species and has not yet reached the expected levels of a non-affected river basin in the southern Iberian Peninsula.
Del Río, Mercedes; Font, Rafael; Almela, Concepción; Vélez, Dinoraz; Montoro, Rosa; De Haro Bailón, Antonio
On 25 April 1998, approximately 4.5 hm(3) of pyritic sludge, containing 5000 mg of As kg(-1) among other pollutants, was spilled into the Agrio and Guadiamar rivers and the surrounding agricultural areas (Aznalcóllar, Seville, Southern Spain). Many trace metals such as Pb, Cu, Zn, Cd, Tl, Sb and As reached the Doñana National Park, the largest wetland area in Europe, affecting soils, different plant and animal species. In order to recuperate the affected lands by employing plants capable of accumulating high levels of contaminants in shoots, periodical field surveys have been made to identify the metal-tolerant species that are spontaneously growing in the polluted soils, and are able to uptake one or various of the contaminants. Among the 99 different plant species studied, Anchusa azurea, Beta vulgaris, Chamaemelum fuscatum, Convolvulus arvensis, Cynodon dactylon, Diplotaxis virgata, Erodium aethiopicum, Lavatera cretica, Malva nicaeensis, Silybum marianum and, above all, Amaranthus blitoides highlight as the most promising to be used in the remediation of the affected area.
Drake, P; Baldó, F; Cuesta, J A; García-González, D; Silva-García, A; Arias, A M; Rodríguez, A; Sobrino, I; Fernández-Delgado, C
The initial effects of the toxic waste spill in April 1998 at the Aznalcóllar mine (SW Spain) on the nektonic community of the Guadalquivir Estuary were examined at three sampling sites using univariate and multivariate techniques. Since studied communities showed a considerable seasonal trend, only seasonally homogenous periods were compared to analyse effects of the spill: May-August 1997 (before spill) and May-August 1998 (after spill). Results of both techniques (two-way nested ANOVA and ANOSIM tests, P > 0.05) indicated that there was no significant difference between the nektonic community of the estuary before and after the spill (monthly number of species, abundance, biomass and similarity among samples). Conversely, an unusually high density was observed at the outer sampling site immediately after the spill for species typical of more stagnant estuarine habitats. This feature seems to indicate that the fauna in the estuarine area through which the untreated water penetrated into the main course may have been disturbed. Results also suggest that this initial sudden input of fresh water to the estuary could have enhanced the effects of an increased river flow (a drop in the salinity). Nevertheless, longer temporal series of data, especially for permanent estuarine inhabitants, are recommended before conclusions can be drawn on the effects of the toxic waste spill on estuarine communities.
Madejón, P; Murillo, J M; Marañón, T; Cabrera, F; López, R
The collapse of the tailing dam in the Aznalcóllar pyrite mine (SW Spain) occurred in April 1998 and affected approximately 4300 ha along the Agrio and Guadiamar valleys. An urgent soil cleaning up and remediation programme was started just after the accident. Eighteen months later, mineral nutrients and trace elements concentration in soil and two wild grasses--Cynodon dactylon and Sorghum halepense--have been studied. Three types of conditions are distinguished: (a) unaffected soils (control); (b) cleaned up and remediated soils (remediated); and (c) sludge-covered soils left in a fenced plot (non-remediated). As, Cd, Cu and Pb in grasses reached toxic levels for the food web in the non-remediated plot, while on remediated soils only Cd reached a toxic level in grass tissues. However, Pb and, to a lesser extent As and Fe, reached also toxic levels in unwashed plants (as they would be ingested by animals) in remediated soils. Both native grasses seem tolerant of trace elements pollution and suitable for stabilisation of spill-affected soils.
Márquez-Ferrando, Rocío; Santos, Xavier; Pleguezuelos, Juan M; Ontiveros, Diego
Quantification of heavy metal concentrations in biota is a common technique that helps environmental managers measure the level of pollutants circulating in ecosystems. Despite interest in heavy metals as indicators of localized pollution, few studies have assessed these pollutants in reptiles. In 1998, the tailing pond of a pyrite mine near Aznalcóllar (southwestern Spain), containing mud with high heavy metal concentrations, collapsed, releasing 6 million m(3) of toxic sludge into the Guadiamar Basin. Here we analyze heavy metal concentrations in the most common reptile in the area, the large psammodromus, Psammodromus algirus, a rather small lizard. We quantified levels of several elements (Hg, Sb, Cd, Cr, Tl, Sn, Ba, Cu, Pb, Sr, Mn, Rb, As, and Zn) in lizard tail clips collected in and around the affected area during the springs of 2005 and 2006. Samples were collected from two contaminated localities, one directly affected by the spill, and another adjacent to the tailing pond, but not covered by toxic mud. We also collected samples from a nonpolluted control site in the same basin. We found higher concentrations of As, Tl, Sn, Pb, Cd, and Cu in lizards from the affected area than in lizards from the control site, indicating the continued presence of heavy metal pollutants in the terrestrial food chain 8 years after the mine accident. We did not uncover sexual or annual differences in heavy metal concentrations, although concentrations increased with lizard size. We discuss how heavy metals moved across the food chain to lizards, despite intensive restoration efforts after the accident, and suggest that reptiles to be included in biomonitoring programs of heavy metals pollution in terrestrial habitats.
Relationships between T-cell-mediated immune response and Pb, Zn, Cu, Cd, and as concentrations in blood of nestling white storks (Ciconia ciconia) and black kites (Milvus migrans) from Doñana (southwestern Spain) after the Aznalcóllar toxic spill.
Baos, Raquel; Jovani, Roger; Forero, Manuela G; Tella, José L; Gómez, Gemma; Jiménez, Begoña; González, María J; Hiraldo, Fernando
In the Aznalcóllar mining accident (April 1998), nearly six million cubic meters of toxic wastes were spilled in the surroundings of the Doñana National Park (southwestern Spain). The present study focused on the likely effects of metal pollution on the immune system of nestling white storks (Ciconia ciconia) and black kites (Milvus migrans) sampled in the nearby area. Using the phytohaemagglutinin skin test, we examined cell-mediated immune response (CMI) in relation to Pb, Zn, Cu, Cd, and As concentrations in blood of 281 nestling white storks and of 89 black kites. The former species was monitored along a four-year period (1999, 2001-2003), while black kites were sampled in 1999. Overall, average levels of heavy metals and As were relatively low when compared to those reported for birds in metal-polluted areas. Copper showed a negative effect on CMI in both species, although the relationship was significant only for white storks in 2002. We found no evidence that environmental exposure to Pb, Zn, As, and Cd had any effect on nestlings' CMI. Interannual consistency is revealed as an important factor, supporting the need of long-term studies when assessing the immunotoxic effects of metal exposure in the wild.
Taggart, M A; Figuerola, J; Green, A J; Mateo, R; Deacon, C; Osborn, D; Meharg, A A
In April 1998, a holding lagoon containing pyrite ore processing waste, failed and released 5-6 million m3 of highly polluting sludge and acidic water. Over 2650 ha of the internationally important Doñana Natural Park became contaminated, along with < 100 ha of the more pristine Doñana National Park. In order to assess the affect of the spill on waterfowl from Doñana, bone and liver samples from 124 individuals have been analysed for As, Pb, Cu, Zn and Se. Five species have been studied, from the Rallidae (rails), Anatini (dabbling ducks) and Aythyini (pochards) families. Geometric mean bone concentrations 2-3 months after the spill were in the order of Zn > Cu > Pb > Se > As, while liver concentrations were in the order of Zn > Cu > Se > Pb > As. Dry weight bone concentrations ranged from n.d-1.76 mg kg(-1) As, 109.4-247.6 mg kg(-1) Zn, 0.06-1.27 mg kg(-1) Se, n.d-134.11 mg kg(-1) Pb, and 2.18-8.92 mg kg(-1) Cu. Wet weight liver concentrations ranged from n.d-0.34 mg kg(-1) As, 29.8-220.1 mg kg(-1) Zn, 0.15-0.85 mg kg(-1) Se, n.d-3.80 mg kg(-1) Pb, and 7.30-742.96 mg kg(-1) Cu. The most important factor related to the accumulation of these metals was commonly species; however, location and sex also had important effects on liver As levels, location and age affected Cu levels, while Zn and Pb were affected by age, sex and location. Birds from Natural Park areas were found to have significantly higher levels of bone Zn, Pb and Cu, and liver As and Cu than birds from National Park areas. Female birds had higher liver As, Zn and Pb than males; whilst adults appeared to have lower bone As and Zn but higher liver Pb than chicks/juveniles. Although metal concentrations were elevated in certain individuals, in the majority of birds studied, they did not reach levels widely considered to be toxic. However, it would appear that As and Cu liver levels (which may be indicative of short-medium term pollutant exposure) were elevated in waterbirds which died in the spill contaminated Natural Park, 2-3 months after the disaster.
García-Luque, E; Forja, J M; Delvalls, T A; Gómez-Parra, A
The spill at 'Los Frailes' caused a large input of metals into the riverine, estuarine and coastal ecosystems. Metal behaviour in natural waters can be studied both by performing field measurements, and by undertaking laboratory simulation experiments. Here is described the behaviour of the heavy metals Zn, Cd, Pb and Cu in the Guadalquivir estuary using incubation experiments and the results compared to those obtained during field assessments. If the toxic waste water had been discharged untreated into the environment, it could have raised the heavy metal concentrations in the estuary water to high values, such as 20.65 microM for Zn and 40 x 10(-3) microM for Cd. These values are several times higher than those obtained in samples collected in the area during the monitoring of the early impact. The metals present a non-conservative behaviour, with a high loss to waters of low salinity values.
Rodríguez-Tovar, F J; Martín-Peinado, F J
Biotic recovery after the Cretaceous-Palaeogene (K-Pg) impact is one unsolved question concerning this mass extinction event. To evaluate the incidence of the K-Pg event on biota, and the subsequent recovery, a recent environmental disaster has been analysed. Areas affected by the contamination disaster of Aználcollar (province of Sevilla, southern Spain) in April 1998 were studied and compared with the K-Pg event. Several similarities (the sudden impact, the high levels of toxic components, especially in the upper thin lamina and the incidence on biota) and differences (the time of recovery and the geographical extension) are recognized. An in-depth geochemical analysis of the soils reveals their acidity (between 1.83 and 2.11) and the high concentration of pollutant elements, locally higher than in the K-Pg boundary layer: values up to 7.0 mg kg(-1) for Hg, 2030.7 mg kg(-1) for As, 8629.0 mg kg(-1) for Pb, 86.8 mg kg(-1) for Tl, 1040.7 mg kg(-1) for Sb and 93.3-492.7 p.p.b. for Ir. However, less than 10 years after the phenomenon, a rapid initial recovery in biota colonizing the contaminated, 'unfavourable', substrate is registered. Nesting of the ant Tapinoma nigerrima (Nylander) has taken place through the tailing layer, with arranged particles from inside the soils showing similar values in pollutant elements as the deep soils. This agrees with recent ichnological evidence of a rapid colonization of the K-Pg boundary layer, classically interpreted as an inhabitable substrate, by organisms with a high independence with respect to substrate features (i.e. Chondrites trace makers). The dramatic consequences of the K-Pg boundary impact and the generalized long-time recovery interpreted after the event (in the order of 10(4)-10(5) years) could have been overestimated due to the absence of a high-temporal resolution in the range of 10(2)-10(3) years.
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Kim, Yong Sok; Kim, Min Jung; Park, Sung Chan; Sohn, Dae Kyung; Kim, Dae Yong; Chang, Hee Jin; Nam, Byung-Ho; Oh, Jae Hwan
Purpose Robotic surgery is expected to have advantages over laparoscopic surgery; however, there are limited data regarding the feasibility of robotic surgery for rectal cancer after preoperative chemoradiotherapy (CRT). Therefore, we evaluated the short-term outcomes of robotic surgery for rectal cancer. Materials and Methods Thirty-three patients with cT3N0-2 rectal cancer after preoperative CRT who underwent robotic low anterior resection (R-LAR) between March 2010 and January 2012 were matched with 66 patients undergoing laparoscopic low anterior resection (L-LAR). Perioperative clinical outcomes and pathological data were compared between the two groups. Results Patient characteristics did not differ significantly different between groups. The mean operation time was 441 minutes (R-LAR) versus 277 minutes (L-LAR, p < 0.001). The open conversion rate was 6.1% in the R-LAR group and 0% in the L-LAR group (p=0.11). There were no significant differences in the time to flatus passage, length of hospital stay, and postoperative morbidity. In pathological review, the mean number of harvested lymph nodes was 22.3 in R-LAR and 21.6 in L-LAR (p=0.82). Involvement of circumferential resection margin was positive in 16.1% and 6.7%, respectively (p=0.42). Total mesorectal excision (TME) quality was complete in 97.0% in R-LAR and 91.0% in L-LAR (p=0.41). Conclusion In our study, short-term outcomes of robotic surgery for rectal cancer after CRT were similar to those of laparoscopic surgery in respect to bowel function recovery, morbidity, and TME quality. Well-designed clinical trials are needed to evaluate the functional results and long-term outcomes of robotic surgery for rectal cancer. PMID:25779367
Matthews, Lynn; Uson, Juan M.
We summarize results from an H I+optical imaging study of the @ Integral Sign @ ] galaxy, UGC 3697. UGC 3697 is a low-mass, Sd spiral that exhibits a @ superthin @ ] disk morphology despite a prounced gasous and stee llar warp. Our new observations show evidence for a recent minor merger in this system that could account for its large-scale warp and a number of other properties of this galaxy. We speculate that UGC 3697 has been caught in a rather short-lived dynamical state, and may soon undergo significant structural and morphological changes.
Hutson, P A; Holgate, S T; Church, M K
We describe the effects of the antiallergic drug cromolyn sodium and the beta 2-selective adrenoceptor agonist albuterol against early and late phase changes in specific airways conductance (sGaw) and leukocyte infiltration into the airways after allergen challenge of nonanesthetized guinea pigs. Inhalation of ovalbumin by sensitized guinea pigs induced three phases of airways obstruction: an early asthmatic response (EAR) peaking at 2 h, a late response (LAR) peaking at 17 h, and a further late response (LLAR) being observed at 72 h. The LAR was accompanied by a 13-fold rise in neutrophils and a four-fold rise in eosinophils recovered by bronchoalveolar lavage (BAL) at 17 h. By 72 h, the BAL content of neutrophils had returned to near normal, whereas eosinophil numbers had risen to 6.7-fold above baseline. Inhalation of an aerosolized solution of cromolyn, 10 mg/ml, 15 min before challenge inhibited both the EAR and LAR and the influx of neutrophils into the airways at 17 h but had no effect on eosinophil accumulation. Inhalation of cromolyn at 6 h, i.e., after the completion of the EAR, inhibited the LAR, the LLAR, and the rise in eosinophils at 72 h but did not reduce the influx of neutrophils at 17 h. Administration of cromolyn at both 15 min before and 6 h after challenge inhibited all changes in sGaw and reduced the accumulation of neutrophils at 17 h and the influx of eosinophils at 72 h. In contrast, inhalation of albuterol, 0.1 mg/ml, 15 min before allergen provocation blocked the EAR and the rise in BAL neutrophils at 17 h but did not inhibit the LAR. Inhalation of albuterol at 6 h partially reversed the LAR but had no effect on either the LLAR or cellular changes. Given at both times, albuterol inhibited the EAR and neutrophil accumulation at 17 h and partially reversed the LAR but produced no other effects.(ABSTRACT TRUNCATED AT 250 WORDS)
between 60 and 77 MPaJm , and reference 20 gives Kic of 44.5 MPa-"lm. "Metallic Materials Properties Development and Standardization [ MMPDS (ref. 8...04 +7.63477e+04 +5.74554e+04÷3.5630e+t04 +i 967 0e+0 4 76217,e+ 02 -1,1142e+04-3.706e0 -5. 363e+04 Max iI.3302533 + 05 ,it ,erei P282•0-2 CnLLAR...Standardization ( MMPDS )," Department of Transportation Report DOT/FAA/AR- MMPDS -01, January 2003. 9. Rice, R.C.; Goode, R.J.; Bakackas, J.G. Jr.; and
Aguilar, J; Dorronsoro, C; Fernández, E; Fernández, J; García, I; Martín, F; Simón, M
Soil pollution was studied after the spill of the Aznalcóllar pyrite mine between 1998 and 2001, analyzing As, Zn, Cd, Cu and Pb both in total concentrations as well as in soluble and bioavailable forms. The main remediation measures were: clean-up of the tailings and polluted soils, plus application of amendment materials (liming). The results indicate that, after three years, 50-70% of the acidic soils and 25-30% of the basic soils are still highly polluted in total arsenic. The limit of 0.04 mg kg(-1) for water-soluble arsenic is exceeded in 15-20% of all soils. The EDTA-extractable arsenic (bioavailable) exceeds the limit of 2 mg kg(-1) only in the acidic sectors. After clean-up, the homogenization of the upper 20-25 cm of the soils appears to be the most recommended measure in the reduction of pollution.
Guerrero, Flor Ma; Lozano, Macarena; Rueda-Cantuche, José M
On 25 April 1998, the mineral waste retaining wall at the Swedish-owned pyrite mine at Aznalcóllar (Seville, Spain) burst, causing the most harmful environmental and socio-economic disaster in the history of the River Guadiamar basin. The damage was so great that the regional government decided in May 1998 to finance a comprehensive, multidisciplinary research initiative with the objective of eradicating or at least minimising all of the negative social, economic and environmental impacts. This paper utilises a Strengths, Weaknesses, Opportunities and Threats (SWOT) analysis to identify eight strategic measures aimed at providing policymakers with key guidelines on implementing a sustainable development model, in a broad sense. Empirical evidence, though, reveals that, to date, major efforts to tackle the negative impacts have centred on environmental concerns and that the socio-economic consequences have not been completely mitigated.
Hita, Raúl; Torrent, José; Bigham, Jerry M
After the collapse on 25 Apr. 1998 of the Aznalcóllar mine tailings dike in southwestern Spain, 45 km2 of the Guadiamar valley were covered by a pyritic sludge containing up to 2% sphalerite (ZnS). Later, the sludge was mechanically removed and calcium carbonate was plowed into the soil to immobilize heavy metals. By June 2001 more than 60% of the sulfides in the residual sludge had oxidized and soil Zn contents reached locally phytotoxic levels. Therefore, the oxidative dissolution of sphalerite in the sludge and other pyritic samples was examined. Flow-through oxidation experiments showed that: (i) about 5 and 17% of the sludge Fe and Zn were in soluble form, respectively, because the sludge sample had been partly oxidized in the field; (ii) the oxidation rates of the residual pyrite and sphalerite were similar; (iii) the overall sulfide oxidation rate was relatively unaffected by the addition of calcite; and (iv) poorly crystalline Fe (hydr)oxides containing Zn in occluded form and Zn (hydroxi)carbonates were formed in the presence of calcite. The rate of oxidation of reference sphalerite greatly increased when it was incorporated in the sludge or in a reference pyrite matrix. This enhancement was due to galvanic interaction because pyrite oxidation was depressed in the presence of sphalerite. Oxidation by Fe3+ ions was less important because the oxidation rates of native sphalerite were not greater at low than at high pH. The fast oxidation rate of sphalerite in the Aznalcóllar sludge indicates a need for quick adoption of remediation measures in similar accidents elsewhere. The use of calcite amendments has little influence on the oxidation rate but does result in the accumulation of Zn in relatively insoluble forms.
Suñer, M A; Devesa, V; Muñoz, O; López, F; Montoro, R; Arias, A M; Blasco, J
To evaluate the impact on fauna of the release of toxic waste from the tailings dam operated by the Boliden Apirsa S.L company at Aznalcóllar, Seville (Spain) a study was carried out of total and inorganic arsenic contents in 164 samples from six different estuary species, including molluscs, crustaceans and fish, collected at six sampling stations distributed along the estuary and mouth of the River Guadalquivir. The contents found, expressed in micrograms per gram wet weight, were as follows. Total arsenic: Crassostrea angulata--giant cupped oyster (2.44 +/- 0.45); Scrobicularia plana--peppery furrow (2.50 +/- 0.73); Palaemon longirostris--delta prawn (1.33 +/- 0.54); Uca tangeri--AfroEuropean fiddler crab (1.76 +/- 0.08); Melicertus kerathurus--shrimp (3.60 +/- 1.92); and Liza ramada--mullet (0.65 +/- 0.38). Inorganic arsenic: C. angulata (0.09 +/- 0.02); S. plana (0.38 +/- 0.23); P. longirostris (0.04 +/- 0.01); U. tangeri (0.22 +/- 0.03); M. kerathurus (0.03 +/- 0.01); and L. ramada (0.03 +/- 0.03). The levels of total As are comparable to those obtained by other authors. With respect to inorganic arsenic, only S. plana and U. tangeri present high levels of inorganic arsenic. This may be due to the fact that these organisms live in estuary sediments, reservoirs of inorganic arsenic, and ingest particles of sediments during feeding. Because of the lack of information for this area concerning previous levels of total and inorganic arsenic in the species analysed, it was not possible to establish the impact on the fauna of the River Guadalquivir estuary of the toxic spill resulting from the failure of the mine tailings dam at Aznalcóllar. With respect to the implications to human health as a result of consumption of species from the Guadalquivir estuary, only with the species Scrobicularia plana, as a high consumption of this mollusc might, in some cases, exceed the maximum tolerable intake for inorganic arsenic indicated by the FAO/WHO. Consumption of the
Kemper, Thomas; Sommer, Stefan
The possibility to adapt chemometrics approaches for the quantitative estimation of heavy metals in soils polluted by a mining accident was explored. In April 1998, the dam of a mine tailings pond in Aznalcóllar (Spain) collapsed and flooded an area of more than 4000 ha with pyritic sludge contaminated with high concentrations of heavy metals. Six months after the end of the first remediation campaign, soil samples were collected for chemical analysis and measurement of visible to near-infrared reflectance (0.35-2.4 microm). Concentrations for As, Cd, Cu, Fe, Hg, Pb, S, Sb, and Zn were well above background values. Prediction of heavy metals was achieved by stepwise multiple linear regression analysis (MLR) and an artificial neural network (ANN) approach. It was possible to predict six out of nine elements with high accuracy. Best R2 between predicted and chemically analyzed concentrations were As, 0.84; Fe, 0.72; Hg, 0.96; Pb, 0.95; S, 0.87; and Sb, 0.93. Results for Cd (0.51), Cu (0.43), and Zn (0.24) were not significant. MLR and ANN both achieved similar results. Correlation analysis revealed that most wavelengths important for prediction could be attributed to absorptions features of iron and iron oxides. These results indicate that it is feasible to predict heavy metals in soils contaminated by mining residuals using the rapid and cost-effective reflectance spectroscopy.
García-Carmona, M; Romero-Freire, A; Sierra Aragón, M; Martínez Garzón, F J; Martín Peinado, F J
Residual soil pollution from the Aznalcóllar mine spill is still a problem in some parts of the affected area, today converted in the Guadiamar Green Corridor. Dispersed spots of polluted soils, identified by the absence of vegetation, are characterized by soil acid pH and high concentrations of As, Pb, Cu and Zn. Ex situ remediation techniques were performed with unrecovered soil samples. Landfarming, Composting and Biopiles techniques were tested in order to immobilize pollutants, to improve soil properties and to promote vegetation recovery. The effectiveness of these techniques was assessed by toxicity bioassays: Lactuca sativa L. root elongation test, Vibrio fischeri bioluminescence reduction test, soil induced respiration test, and Eisenia andrei survival and metal bioaccumulation tests. Landfarming and Composting were not effective techniques, mainly due to the poor improvement of soil properties which maintained high soluble concentrations of Zn and Cu after treatments. Biopile technique, using adjacent recovered soils in the area, was the most effective action in the reduction of soil toxicity; the improvement of soil properties and the reduction in pollutants solubility were key to improve the response of the tested organisms. Therefore, the mixture of recovered soils with polluted soils in the areas affected by residual contamination is considered a more suitable technique to reduce the residual pollution and to promote the complete soil recovery in the Guadiamar Green Corridor. Copyright © 2016 Elsevier Ltd. All rights reserved.
Fernández-Gálvez, J; Barahona, E; Iriarte, A; Mingorance, M D
Groundwater represents a very significant source of fresh water for irrigation and drinking purposes and therefore preserving the availability and quality of this resource is extremely important. A first assessment of the amount of pollutants that can be exported to groundwater via soil drainage can be made by a) measuring the amount of contaminants present in the soil solution at the bottom of the soil after a prolonged simulated rainfall event, and b) estimating the amount of drainage water passing the soil bottom during a period of time long enough to include sufficient instances of both, wet and dry episodes inherent to the local climate. Drainage water was estimated by means of a simple infiltration model ("bucket model") which computes on a daily basis the inputs and outputs of soil water through rainfall and evapotranspiration generated by a stochastic model of the local climate along a period of 50-100 years. The methodology was applied in the Guadiamar valley after the toxic spill of a pyrite mine in Aznalcóllar (Spain). The results show that Zn is the dominant contaminant at the site with a 1.2 g m(-2)year(-1) contribution to groundwater. The presence of a gravel rich horizon below 50 cm depth reveals an increase in drainage and the threat to groundwater.
Blasco, J; Arias, A M; Sáenz, V
After the Aznalcóllar mining spill (25th April 1998), considerable social concern arose amongst the inhabitants of the SW Iberian Peninsula concerning the consumption of local seafood. Squilla mantis was collected in four regions of the Gulf of Cádiz with a dual objective: to analyze the heavy metal levels for human consumption and as part of biomonitoring program. Heavy metal concentrations (Fe, Mn, Zn, Cu, Cd and Pb) were analyzed in soft tissues and cuticle. The highest values were found in the soft tissues for zinc, copper and cadmium and in the cuticle for iron, manganese and lead. The mean copper concentration in the soft tissue, corresponding to the edible part, was 27.1 microg x g(-1) wet weight. Approximately 80% of stations showed values higher than 20 microg x g(-1) wet weight of copper, the Spanish legal limit for the concentration of this metal in the crustacean for human consumption. For Zn and Cu no significant differences were found between regions, probably related with the capacity for regulation of S. mantis. The highest values found for copper in the Gulf of Cádiz compared to other areas is likely to be related with contamination from terrestrial mining activities (copper and pyrites) in the region, dating back to the times of Tartessians and Romans, rather than the effects of mining spill which was shown not to create any significant increases in heavy metal concentrations of organisms of the Guadalquivir River or the adjacent coastal area.
Martín, Francisco; Diez, María; García, Inés; Simón, Mariano; Dorronsoro, Carlos; Iriarte, Angel; Aguilar, José
In the present work, soil profiles were sampled 40 days and three years after an accidental pyrite tailing spill from the Aznalcóllar mine (S Spain) in order to figure out the effects of the acidic solution draining from the tailing. The composition of the acidic solution, the mineralogy, and the total and soluble content of the major elements were analysed at varying depths. The results show a weathering process of carbonates and of primary silicates. Calcium released is leached or reacts with the sulphate ions to form gypsum. Magnesium, aluminium and potassium tend to leach from the uppermost millimetres of the soil, accumulating where the pH>/=5.0; also the iron, probably forming more or less complex hydroxysulphates, precipitate in the upper 5 cm. The strong releasing of soluble salts increases the electrical conductivity, while the soluble potassium tends to decrease in the uppermost part of the soil due to the neoformation of jarosite. Iron is soluble only where the pH=2.3, and aluminium where the pH=5.5.
Clemente, Rafael; Almela, Concepción; Bernal, M Pilar
Phytoremediation of metal-polluted soils can be promoted by the proper use of soil amendments and agricultural practices. A 4-year phytoremediation programme was applied to a site affected by the toxic spill of pyrite residue at Aznalcóllar (Spain) in 1998, contaminated with heavy metals (Zn, Cu, Pb, Cd) and arsenic. This consisted of active phytoremediation, using organic amendments (cow manure and compost) and lime and growing two successive crops of Brassica juncea (L.) Czern., followed by natural attenuation without further intervention. Changes in soil pH, extractable metal and As concentrations, organic carbon content and microbial biomass was evaluated. The initial oxidation of metal sulphides from pyrite residues released soluble metals and reduced soil pH to extremely acidic values (mean 4.1, range 2.0-7.0). The addition of lime (up to 64 t ha(-1)) increased soil pH to adequate values for plant growth, resulting in a significant decrease in DTPA-extractable metal concentrations in all plots. The natural attenuation phase showed also a decrease in extractable metals. Organic treatments increased the soil total organic carbon, which led to higher values of microbial biomass (11.6, 15.2 and 14.9 g kg(-1) TOC and 123, 170 and 275 microg g(-1) biomass-C in control, compost and manure plots, respectively). Active phytoremediation followed by natural attenuation, was effective for remediation of this pyrite-polluted soil.
Vázquez, S; Carpena, R O; Bernal, M P
White lupin (Lupinus albus L.) is an annual crop that has been used for phytostabilization of acidified multi-contaminated soils. Once the culture cycle is over, after shoot harvesting, a progressive transference of contaminants from roots to soil may take place as decomposition of roots occurs. An incubation experiment with Cu, Zn, Cd, and As-loaded roots of white lupin and soils with different pH values and concentrations of these contaminants from the area affected by a mine spill at Aznalcóllar (near Seville, Spain) was performed in order to assess the effect of the decomposition of the roots to the pH and (NH4)2SO4-extractable levels of these pollutants in the soils. Pollutants loaded-roots were mineralized (56 d) at a ratio similar to animal manures (15.8-19.4% of total organic carbon) in soil. The estimated root inputs of contaminants in comparison to their extractable concentrations in soil were high, especially in the control, non-contaminated and neutral contaminated soils. However, the extractable concentrations of the toxic elements in the soil were mainly governed by soil pH. Hence, the correction and maintenance of the soil pH within the range 5-6 after lupin culture is essential for long-time phytostabilization of acidified multi-contaminated soils.
Gibert, Oriol; Cortina, José Luis; de Pablo, Joan; Ayora, Carlos
A permeable reactive barrier (PRB) was installed in Aznalcóllar (Spain) in order to rehabilitate the Agrio aquifer groundwater severely contaminated with acid mine drainage after a serious mining accident. The filling material of the PRB consisted of a mixture of calcite, vegetal compost and, locally, Fe(0) and sewage sludge. Among the successes of the PRB are the continuous neutralisation of pH and the removal of metals from groundwater within the PRB (removals of >95%). Among the shortcomings are the improper PRB design due to the complexity of the internal structure of the Agrio alluvial deposits (which resulted in an inefficient capture of the contaminated plume), the poor degradability of the compost used and the short residence time within the PRB (which hindered a complete sulphate reduction), the clogging of a section of the PRB and the heterogeneities of the filling material (which resulted in preferential flows within the PRB). Undoubtedly, it is only through accumulated experience at field-scale systems that the potentials and limits of the PRB technology can be determined.
Sánchez-Chardi, Alejandro; Ribeiro, Ciro Alberto Oliveira; Nadal, Jacint
Historically impacted by anthropogenic activities, the nature reserve of Doñana (SW Spain) was affected by an unprecedented spillage of mud and acidic water from the Aznalcóllar pyrite mine in April 1998. Although several studies have addressed the influence of this spill on soils, water, and biota, there is little information on mammals, especially carnivorous species. We measured the concentrations of Fe, Mg, Pb, Hg, Cd, Zn, Cu, Mn, Mo, Co, and Cr in specimens of the greater white-toothed shrew, Crocidura russula, inhabiting the protected area affected by the mine spillage. We also examined other parameters to approach at the physiological effects of pollution. We found an increase in non-essential metals (Pb, Cd, and Hg), and morphometric, histological and genotoxic alterations. Age and gender were two significant factors explaining metal bioaccumulation: adults had higher Hg and Cd levels than juveniles, whereas males bioaccumulated more Pb and Co and less Mo than females. The micronucleus frequencies in blood erythrocytes were significantly higher in specimens from the polluted site than animals from the control site. Shrews from the impacted area also had hepatic alterations, namely increased liver-body ratio, focal necrosis, and signs of apoptosis in hepatocytes. Due to the relevance of small mammals in the diet of endangered species such as carnivorous birds and mammals, the findings of our study are of practical use for the management of the Doñana wildlife reserve and other protected Mediterranean wetlands.
Nakamaru, Yasuo Mitsui; Martín Peinado, Francisco José
We evaluated the long-term (18 year) and short-term (4 weeks) changes of Sb in contaminated soil with SOM increase under remediation process. In the Aznalcóllar mine accident (1998) contaminated area, the remediation measurement implemented the Guadiamar Green Corridor, where residual pollution is still detected. Soils of the re-vegetated area (O2) with high pH and high SOM content, moderately re-vegetated area (O1) and unvegetated area (C) were sampled. Soil pH, CEC, SOM amount and soil Sb forms were evaluated. Soil Sb was measured as total, soluble, exchangeable, EDTA extractable, acid oxalate extractable, and pyro-phosphate extractable fractions. Further, the short-term effect of artificial organic matter addition was also evaluated with incubation study by adding compost to the sampled soil from C, O1 and O2 areas. After 4 weeks of incubation, soil chemical properties and Sb forms were evaluated. In re-vegetated area (O2), soil total Sb was two times lower than in unvegetated area (C); however, soluble, exchangeable, and EDTA extractable Sb were 2-8 times higher. The mobile/bioavailable Sb increase was also observed after 4 weeks of incubation with the addition of compost. Soluble, exchangeable, and EDTA extractable Sb was increased 2-4 times by compost addition. By the linear regression analysis, the significantly related factors for soluble, exchangeable, and EDTA extractable Sb values were pH, CEC, and SOM, respectively. Soluble Sb increase was mainly related to pH rise. Exchangeable Sb should be bound by SOM-metal complex and increased with CEC. EDTA extractable fraction should be increased with increase of SOM as SOM-Fe associated Sb complex. From these results, it was shown that increase of SOM under natural conditions or application of organic amendment under remediation process should increase availability of Sb to plants. Copyright © 2017 Elsevier Ltd. All rights reserved.
Vanderlinden, Karl; Polo, Maria J; Ordóñez, Rafaela; Giráldez, Juan
The residual pollution after the Aznalcóllar (southwestern Spain) pyrite mine spill is still a threat due to the continuing oxidation of sulfuric minerals. The objective of this paper was to analyze the combined effect of pyrite oxidation, sugar beet foam applications, and meteorological conditions on the spatiotemporal evolution of the pH and EDTA-extractable Zn concentration, using non co-located data from 11 sampling dates between June 1999 and March 2002. Median pH values ranged from 4.4 at the beginning of the monitoring period to 7.6 at the end, although values near 2.5 were observed throughout the entire period, despite of two sugar beet foam (SBF) applications. Zinc distributions were positively skewed and median concentrations ranged from 17 to 94 mg kg(-1). The inverse relationship between pH and Zn became weaker toward the end of the monitoring period as a consequence of the precipitation and posterior dissolution of newly formed minerals from the reaction products of the pyrite oxidation. Normal score maps showed that after the SBF applications only 0.5% of the monitored area was below the pH = 4 threshold, while on other dates up to one-third of the area remained below this value. The better performance of the second SBF application could be explained in terms of pyrite oxidation pathways and environmental conditions. From this analysis, with data obtained under uncontrolled field conditions, it is concluded that SBF should be applied before or during the wet and cold season to alleviate acidification, caused by the oxidation of pyrite or other sulfuric minerals.
Baos, Raquel; Blas, Julio; Bortolotti, Gary R.; Marchant, Tracy A.; Hiraldo, Fernando
Background/Objective Endocrine parameters have proven useful in the detection of early or low-level responses to pollutants. Although most of the studies on endocrine modulation have been focused on processes involving gonadal steroids, contaminants may target other parts of the endocrine system as well. In this study we examined the adrenocortical stress response and thyroid hormone status in free-living nestling white storks (Ciconia ciconia) in relation to heavy metals (zinc, lead, copper, cadmium) and arsenic levels in blood. Methods Fieldwork was conducted in an area polluted by the Aznalcóllar mine accident (southwestern Spain) and in a reference site. We used a standardized capture, handling, and restraint protocol to determine both baseline and maximum plasma corticosterone. Circulating levels of thyroxine (T4) and triiodothyronine (T3) were also measured. Results No effects of metals or As were found on baseline corticosterone, but maximum levels of corticosterone were positively related to Pb in both locations. This relationship was stronger in single nestlings than in birds from multiple-chick broods, which suggests a greater impact of Pb on more stressed individuals. Metal pollution did not affect plasma T4 or T3 levels, although thyroid status differed with location. Conclusions Because a compromised hypothalamus–pituitary–adrenal (HPA) function can have far-reaching consequences in terms of altered behavioral and metabolic processes necessary for survival, our results suggest that birds exposed to sublethal Pb levels may be at risk through an altered adrenocortical stress response, and further support the idea that HPA axis-related end points might be useful indicators of metal exposure and potential toxicity in wild animals. PMID:17035132
Solà, Carolina; Burgos, María; Plazuelo, Angel; Toja, Julia; Plans, Marc; Prat, Narcís
In the 1998 Aznalcóllar mining accident, 5 million cubic meters of toxic waste were spilled into the Guadiamar River (SW Spain). This paper describes the likely effects of metal pollution on the macroinvertebrate community in the first 15 km of the river adjacent to the mine, 2 years after the spill. The contents of Zn, Cu, Pb, As, Cd, Tl, and Sb in water, sediment, and in the caddisfly Hydropsyche were analysed, together with some physico-chemical parameters. From the results of physico-chemical and community parameters, the studied area was divided into three sections: the first section contained upstream control stations, not affected by current mining activities, and with a diverse macroinvertebrate community structure (mean number of families = 19); the second section, close to the mine, was severely polluted, with more than 50 mg l(-1) of Zn or 1.6 mg l(-1) of Cu in water, a pH of nearly 4, and a very diminished macroinvertebrate community (three families); in the last section, 6-15 km downstream from the mine, the water quality improved, metal concentrations decreased, pH reached neutrality and the macroinvertebrate community comprised eight families. We also determined metal concentrations in the larvae of Hydropsyche and found increases of 3- to 35-fold (for Cu and Cd, respectively) compared to control sites. As far as we are aware, these values are the highest concentrations so far detected in this caddisfly anywhere in the world. Different patterns of metal and pH tolerance were identified in macroinvertebrates. Most of the species were intolerant to present pollution levels and were only present in control sites. Others were tolerant to metal pollution but not to low pH and were present in the main river downstream of the mine, while a very few species managed to live in the most polluted section, with very low pH and high metal concentrations.
Zhou, Zong-Guang; Wang, Zhao; Yu, Yong-Yang; Shu, Ye; Cheng, Zhong; Li, Li; Lei, Wen-Zhang; Wang, Tian-Cai
AIM: To assess the feasibility and efficacy of laparoscopic total mesorectal excision (LTME) of low rectal cancer with preservation of anal sphincter. METHODS: From June 2001 to June 2003, 82 patients with low rectal cancer underwent laparoscopic total mesorectal excision with preservation of anal sphincter. The lowest edge of tumors was below peritoneal reflection and 1.5-7 cm from the dentate line (1.5-5 cm in 48 cases, 5-7 cm in 34 cases). RESULTS: LTME with anal sphincter preservation was performed on 82 randomized patients with low rectal cancer, and 100% sphincter preservation rate was achieved. There were 30 patients with laparoscopic low anterior resection (LLAR) at the level of the anastomosis below peritoneal reflection and 2 cm above from the dentate line; 27 patients with laparoscopic ultralow anterior resection (LULAR) at the level of anastomoses 2 cm below from the dentate line; and 25 patients with laparoscopic coloanal anastomoses (LCAA) at the level of the anastomoses at or below the dentate line. No defunctioning ileostomy was created in any case. The mean operating time was 120 min (ranged from 110-220 min), and the mean operative blood loss was 20 mL (ranged from 5-120 mL). Bowel function was restored and diet was resumed on day 1 or 2 after operation. The mean hospital stay was 8 d (ranged from 5-14). Postoperative analgesics were used in 45 patients. After surgery, 2 patients had urinary retention, one had anastomotic leakage, and another 2 patients had local recurrence one year later. No interoperative complication was observed. CONCLUSION: LTME with preservation of anal sphincter is a feasible, safe and minimally invasive technique with less postoperative pain and rapid recovery, and importantly, it has preserved the function of the sphincter. PMID:12854145
Moreno-Jiménez, Eduardo; Vázquez, Saúl; Carpena-Ruiz, Ramón O; Esteban, Elvira; Peñalosa, Jesús M
Re-vegetation is the main aim of ecological restoration projects, and in Mediterranean environments native plants are desirable to achieve successful restoration. In 1998, the burst of a tailings dam flooded the Guadiamar river valley downstream from Aznalcóllar (Southern Spain) with sludges that contained elevated concentrations of metals and metalloids, polluting soils and waters. A phytoremediation experiment to assess the potential use of native shrub species for the restoration of soils affected by the spillage was performed from 2005 to 2007, with soils divided into two groups: pH < 5 and pH > 5. Four native shrubs (Myrtus communis, Retama sphaerocarpa, Rosmarinus officinalis and Tamarix gallica) were planted and left to grow without intervention. Trace element concentrations in soils and plants, their extractability in soils, transfer factors and plant survival were used to identify the most-interesting species for phytoremediation. Total As was higher in soils with pH < 5. Ammonium sulphate-extractable zinc, copper, cadmium and aluminium concentrations were higher in very-acid soils, but arsenic was extracted more efficiently when soil pH was >5. Unlike As, which was either fixed by Fe oxides or retained as sulphide, the extractable metals showed significant relationships with the corresponding total soil metal concentration and inverse relationships with soil pH. T. gallica, R. officinalis and R. sphaerocarpa survived better in soils with pH > 5, while M. communis had better survival at pH < 5. R. sphaerocarpa showed the highest survival (30%) in all soils. Trace element transfer from soil to harvestable parts was low for all species and elements, and some species may have been able to decrease trace element availability in the soil. Our results suggest that R. sphaerocarpa is an adequate plant species for phytostabilising these soils, although more research is needed to address the self-sustainability of this remediation technique and the
Riba, I; Blasco, J; Jiménez-Tenorio, N; Delvalls, T Angel
The bioaccumulation of six metals (Fe, Mn, Zn, Cd, Pb and Cu) was studied as part of the monitoring of the Aznalcóllar mining spill (April 1998) on the Guadalquivir estuary and in other estuaries located in the Gulf of Cádiz. Fish, clams and oysters were collected during different seasonal periods along the years 2000 and 2001 in the Guadalquivir estuary to determine the bioaccumulation of the metals originated by the mining spill. Results were compared to the bioaccumulation of the same metals in fish and clams exposed in the laboratory to sediments collected in the same areas during autumn 2001. The bioaccumulation of these metals was compared to the concentration of metals measured in tissues of same taxas collected in the areas of the ria of Huelva and the Bay of Cádiz. Results show that the bioaccumulation of Zn and Cd in the organisms sampled in the Guadalquivir estuary was associated with the enrichment of these metals in the estuary from the mining spill and decreased along the time reaching the lowest values in autumn 2001. The metal Cu show different trends that are associated with other sources of contamination than the spill and related to the transport of this metal from Huelva to Guadalquivir estuary and/or to the use of this metal as plaguicide in the rice fields located in the area. The comparison between bioaccumulation results under field and laboratory conditions obtained in the different areas of study shows that these data can be used to discriminate between acute and chronic impacts associated with mining activities.
Pérez-Mayol, Sílvia; Blasco, Julián; Tornero, Victoria; Morales-Nin, Beatriz; Massanet, Ana; Tovar-Sánchez, Antonio
The rupture of a mine dam in Aznalcóllar (SW Spain) in April 1998 entailed the contamination of Guadalquivir River and its estuary. To study the ability of bivalve shells to monitor the temporal changes on metal composition in the area, two year old Scrobicularia plana were obtained from two different locations of the estuary (Pantalan highly influenced and Pantoca less influenced) during the year 2000 and 2007. Co, Hg, Mo, Ni and Zn content was measured in shell and soft tissue of S. plana. Metal composition in shells sampled by micromilling and corresponding to the years 1999, 2000, 2006 and 2007 was higher in Pantalan (Co: 5.88 +/- 2.7 microg g(-1); Hg: 0.04 +/- 0.03 microg g(-1); Mo: 0.41 +/- 7.90 microg g(-1); Ni: 37.66 +/- 25.56 microg g(-1) and Zn: 9.19 +/- 8.88 microg g(-1)) than in Pantoca (Co: 3.64 +/- 0.50 microg g(-1); Hg: 0.02 +/- 0.02 microg g(-1); Mo: 4.70 +/- 1.20 microg g(-1); Ni: 7.21 +/- 13.60 microg g(-1) and Zn: 3.90 +/- 1.89 microg g(-1)). A marked temporal decrease was observed for all metals in Pantalan station with concentrations of Co, Hg, Mo, Ni and Zn varying respectively from 7.35 +/- 3.02, 0.05 +/- 0.03, 19.90 +/- 2.40, 70.58 +/- 21.94 and 18.04 +/- 0.98 microg g(-1), in 1999 to 3.07 +/- 1.08, 0.009 +/- 0.001, 2.40 +/- 1.43, 10.11 +/- 3.80 and 1.11 +/- 0.33 microg g(-1) in 2007, indicating that the effect of the mine accident had diminished significantly. Metal content in soft tissues did not follow the same decreasing trend indicating that soft tissues present a different capacity to accumulate metals from the environment. Our results confirm that micromilling shells are a suitable tool to assess bioaccumulation ofcontaminants during the entire life-span of bivalves.
Hinojosa, M Belén; Carreira, José A; Rodríguez-Maroto, José M; García-Ruíz, Roberto
A laboratory study was conducted to evaluate the response of soil enzyme activities (acid and alkaline phosphatase, beta-glucosidase, arylsulfatase, urease and dehydrogenase) to different levels of trace elements pollution in soils representative of the area affected by the pyrite sludge mining spill of Aznalcóllar (Guadiamar basin, SW Spain). Three uncontaminated soils from the study area were mixed with different loads of pyrite sludge to resemble field conditions and criteria applied for reclamation practices following the pollution incident: 0% ("reference" or background level), 1.3% ("attention level", further monitoring required), 4% ("intervention level", further cleaning and liming required) and 13% (ten times the "attention level"). Enzyme activities were analysed 4, 7, 14, 21, 34 and 92 days after pollutant addition and those measured after 92 days were used to calculate the ecological dose value (ED50). Soil enzyme activities and pH decreased after the pyrite sludge addition with respect to the "reference level" (0% pyrite sludge), whereas soil bioavailable (DTPA-extractable) trace elements concentration increased. Arylsulfatase, beta-glucosidase and phosphatase activities were reduced by more than 50% at 1.3% pyrite sludge dose. Arylsulfasate was the most sensitive soil enzyme (in average, ED50=0.99), whereas urease activity showed the lowest inhibition (in average, ED50=7.87) after pyrite sludge addition. Our results showed that the ecological dose concept, applied to enzyme activities, was satisfactory to quantify the effect of a multi-metalic pollutant (pyrite sludge) on soil functionality, and would provide manageable data to establish permissible limits of trace elements in polluted soils. Additionally, we evaluate the recovery of enzyme activities after addition of sugar-beet lime (calcium carbonate) to each experimentally polluted soil. The amount of lime added to each soil was enough to raise the pH to the original value (equal to control soil
Querol, X; Alastuey, A; Lopez-Soler, A; Plana, F; Mesas, A; Ortiz, L; Alzaga, R; Bayona, J M; de la Rosa, J
High levels of atmospheric contamination due to the re-suspension of pyrite particles from the mining waste slurry were recorded in the Guadiamar valley (the Guadiamar is a tributary of the Guadalquivir river) after the toxic spill of Aznalcóllar, north of the Doñana Natural Park (SW Spain). Major high-particulate events occurred during the extraction of the pyrite-rich mud layer, which covered an extensive area of the valley downstream of the confluence of the Agrio and Guadiamar rivers. This study deals with the monitoring of the ambient air quality at two stations near the village of Aznalcázar in the central part of the flooded area. Although the Spanish legal limit for atmospheric particles and lead in environmental air were not exceeded, high daily levels of total suspended particles (TSP) and of some elements with an environmental significance (As, Cd, Cu, Mn, Ni, Pb, Sn, Tl and Zn) were recorded at Aznalcázar and in the Guadiamar valley during soil reclamation (July-August 1998). Despite a progressive decrease in TSP levels through September-October 1998, background was higher than the levels for the May-June period. Evolution of levels for most of the elements studied showed a similar trend. The exceptions were copper, which was partially increased by other emission sources such as fumigation activities, and sodium, which remained at relatively constant levels during the study period because of its marine origin. The physico-chemical characterisation of the atmospheric particulates allowed us to determine the major grain size modes of the pyrite related elements and the solubility of the potentially toxic elements, and to identify the major particulate types present in the atmosphere in the area. Secondary and tertiary aromatic amines (i.e. alkyldiphenylamines and phenylcarbazoles, respectively) were identified in the suspended particles and in the vapour phase collected at the same station as the TSP samples. As some of these aromatic amines had been
Simón, M; Martín, F; Ortiz, I; García, I; Fernández, J; Fernández, E; Dorronsoro, C; Aguilar, J
On the 25th April 1998, toxic water and tailings from a pyrite mine of Aznalcóllar (southern Spain) spilled into the Agrio and Guadiamar River Basin affecting some 40 km2. In five sectors throughout the basin, we monitored the physical and chemical properties of the tailings as well as the degree of pollution in the soils on four different sampling dates: 5 May, 20 May, 4 June and 22 July 1998. The characteristics of the tailings deposited on the soils are shown to be related to distance from the spill. The oxidation rate of the tailings and the solubilization of the pollutant elements were more pronounced in the middle and lower sectors of the basin, where the particle size was finer, the sulfur content higher and the bulk density less. The increases in water-soluble sulfates, Zn. Cd and Cu were very rapid (the highest values being reached 25 days after the spill) and intense (reaching 45% of the total Cu, 65% of the total Zn and Cd). Meanwhile, the increases in water-soluble As, Bi, Sb, Pb and Tl were far lower (ranging between 0.002% of the total Tl and 2.5% of the total As) and less rapid in the case of As, Bi and Pb (the highest values for these elements being reached 40 days after the spill). These soluble elements infiltrated the soils with the rainwater, swiftly augmenting the soil pollution. Twenty-five days after the spill, when the rainfall ranged between 45 and 63 mm, the first 10-cm of the soils in the middle and lower sectors of the basin exceeded the maximum concentration permitted for agricultural soils in Zn, Cu and Tl. At 40 days after the spill, when the rainfall ranged between 60 and 89 mm, all the soils reached or exceeded the maximum permitted concentrations for As and Tl. Nevertheless, the pollutants tended to concentrate in the first 10 cm of the soils without seriously contaminating either the subsoil or the groundwaters. Consequently, a rapid removal of the tailings and the ploughing of the first 25-30 cm of the soils would be urgent
Kulaç, İbrahim; Demir, Çetin; Büyükaşık, Yahya; Kutluk, Tezer; Üner, Aysegül
Amaç: Kronik lenfositik lösemi (KLL) erişkin bireylerde en sık görülen lenfoproliferatif hastalıktır. Bu çalışmanın amacı KLL tanısı almış hastaların doku örneklerindeki proliferasyon merkezlerinin yaygınlığı ve p53 ekspresyonu ile prognozları arasında bağlantı olup olmadığını araştırmaktır. Gereç ve Yöntem: Bu çalışma kapsamında Hacettepe Üniversitesi Tıp Fakültesi Hastanesi Patoloji Anabilim Dalı’nda 2000-2013 yılları arasında KLL tanısı almış̧ 51 hastanın 54 biyopsi örneği yeniden değerlendirilmiştir. Hastaların klinik ve demografik verileri hasta veri tabanından elde edilmiştir. Yapılan incelemede biyopsi örneklerinde proliferasyon merkezlerinin tüm biyopsi alanına oranı (PM/TBA) yarı niceleyici olarak değerlendirilmiş ve seçilen temsili bloklardan elde edilen kesitlerde immünohistokimyasal yöntemle p53 ekspresyonuna bakılmıştır. Sonuç: Hastalar Rai evrelerine göre düşük ve yüksek olmak üzere iki gruba ayrıldığında düşük evreli hastaların genel sağ kalım sürelerinin yüksek evreli hastalara göre daha uzun olduğu görülmüştür (p= 0,030). Ancak, proliferasyon merkezi oranı veya p53 ekspresyon düzeyleri arasında istatistiksel olarak anlamlı ilişki gösterilememiştir. Tartışma: Çalışmamıza dahil edilen hasta grubunda PM/TBA oranı ve P53 immunpozitifliginin sağ kalım ile ilişkisi olmadığı görülmüştür.
Baos, Raquel; Jovani, Roger; Serrano, David; Tella, José L.; Hiraldo, Fernando
Background/Objective Exposure to environmental contaminants may result in reduced reproductive success and long-lasting population declines in vertebrates. Emerging data from laboratory studies on model species suggest that certain life-stages, such as development, should be of special concern. However, detailed investigations of long-term consequences of developmental exposure to environmental chemicals on breeding performance are currently lacking in wild populations of long-lived vertebrates. Here, we studied how the developmental exposure to a mine spill (Aznalcóllar, SW Spain, April 1998) may affect fitness under natural conditions in a long-lived bird, the White Stork (Ciconia ciconia). Methodology The reproductive performance of individually-banded storks that were or not developmentally exposed to the spill (i.e. hatched before or after the spill) was compared when these individuals were simultaneously breeding during the seven years after the spill occurred (1999–2005). Principal Findings Female storks developmentally exposed to the spill experienced a premature breeding senescence compared with their non-developmentally exposed counterparts, doing so after departing from an unusually higher productivity in their early reproductive life (non-developmentally exposed females: 0.5±0.33SE fledglings/year at 3-yr old vs. 1.38±0.31SE at 6–7 yr old; developmentally exposed females: 1.5±0.30SE fledglings/year at 3-yr old vs. 0.86±0.25SE at 6–7 yr old). Conclusions/Significance Following life-history theory, we propose that costly sub-lethal effects reported in stork nestlings after low-level exposure to the spill-derived contaminants might play an important role in shaping this pattern of reproduction, with a clear potential impact on population dynamics. Overall, our study provides evidence that environmental disasters can have long-term, multigenerational consequences on wildlife, particularly when affecting developing individuals, and warns about the
del Mar Montiel Rozas, María; Panettier, Marco; Madejón Rodríguez, Paula; Madejón Rodríguez, Engracia
Nowadays, the study of global C cycle and the different natural sinks of C have become especially important in a climate change context. Fluxes of C have been modified by anthropogenic activities and, presently, the global objective is the decrease of net CO2 emission. For this purpose, many studies are being conducted at local level for evaluate different C sequestration strategies. These techniques must be, in addition to safe in the long term, environmentally friendly. Restoration of contaminated and degraded areas is considered as a strategy for SOC sequestration. Our study has been carried out in the Guadiamar Green Corridor (Seville, Spain) affected by the Aznalcóllar mining accident. This accident occurred 16 years ago, due to the failure of the tailing dam which contained 4-5 million m3 of toxic tailings (slurry and acid water).The affected soils had a layer of toxic sludge containing heavy metals as As, Cd, Cu, Pb and Zn. Restoration techniques began to be applied just after the accident, including the removal of the toxic sludge and a variable layer of topsoil (10-30 cm) from the surface. In a second phase, in a specific area (experimental area) of the Green Corridor the addition of organic amendments (Biosolid compost (BC) and Leonardite (LE), a low grade coal rich in humic acids) was carried out to increase pH, organic matter and fertility in a soil which lost its richest layer during the clean-up operation. In our experimental area, half of the plots (A) received amendments for four years (2002, 2003, 2006 and 2007) whereas the other half (B) received amendments only for two years (2002-2003). To compare, plots without amendments were also established. Net balance of C was carried out using values of Water Soluble Carbon (WSC) and Total Organic Carbon (TOC) for three years (2012, 2013 and 2015). To eliminate artificial changes carried out in the plots, amendment addition and withdrawal of biomass were taken into account to calculate balance of kg TOC
López-Martín, María; Knicker, Heike
Fires lead to formation of the pyrogenic organic matter (PyOM) which is quickly incorporated into the soil. The charring process involves chemical alterations of the litter material, where biologically available structures are transferred into aromatic polymers, such as black carbon (BC) and black nitrogen (BN). In order to reveal the medium term fate of BC and BN in soils, the top 5 cm of A horizons from unburnt, single and double burnt Cambisols of the Sierra de Aznalcóllar (Southern Spain) were collected 7 year after an intense fire and separated according to their density and their size (Golchin et al., 1994; Sohi et al., 2001). The density fractionation yielded in the free (fPOM), occluded particulate organic matter (oPOM) and the mineral-association organic fraction (MAF) and was performed using a sodium polytungstate solution with a density of 1.8 g cm-3. The MAF was further separated into the sand (2 mm to 63 μm) and coarse silt (63 to 20 μm) and fine fraction (< 20 μm) by wet sieving. Organic carbon (Corg) and total nitrogen (Nt) were determined by dry combustion (975°C). The chemical composition was examined by solid-state 13C and 15N NMR spectroscopy. The 13C and 15N NMR spectra of all fPOM and oPOM fractions are dominated by signals assignable to O-alkyl C followed by resonance lines of alkyl C. The spectra indicate that fPOM is mainly composed of undecomposed plant debris whereas oPOM is rich in unsubstituted-aliphatic material. The lack of intensity in the chemical shift region from 160 to140 ppm in the spectra of the small size fractions reveals the absence of lignin residues. This, their low C/N ratios and the clear 13C-signal attributed to carboxylic C allows the conclusion that this fraction mainly composed of microbial residues. Former studies evidenced that aromaticity of the burnt bulk soil decreased with elapsing time after the fire. The present investigation revealed that most of the remaining aromatic C accumulated in the POM fractions
Çetin, Güven; Çıkrıkçıoğlu, M Ali; Özkan, Tuba; Karatoprak, Cumali; Ar, M Cem; Eşkazan, Ahmet Emre; Ayer, Mesut; Cerit, Abdullah; Gözübenli, Kübra; Uysal, Betül Börkü; Erdem, Simge; Ergül, Nurhan; Tatar, Gamze; Çermik, T Fikret
Amaç: Positron emisyon tomografi ve bilgisayarlı tomografi (PET/CT) lenfomanın tedavi ve evreleme algoritmasının önemli bir parçası oldu. Biz çalışmamız da agresiv seyirli non Hodgkin lenfoma (aNHL) ve Hodgkin lenfomalı (HL) hastalarda kemik iliği tutulumunu göstermede kemik iliği biyopsisi (BMB) ile PET/CT sonuçlarını karşılaştırmayı amaçladık. Gereç ve Yöntemler: Çalışmaya 2008-2012 yılları arasında İstanbul’daki 3 büyük hastanede HL ve aNHL tanısı konulan 297 hasta belirlendi. Bu hastaların dosyası retrospektif olarak tarandı ve çalışma kriterlerine uygun 161 hasta çalışmaya alındı. Hastaların başlangıç evrelemesi için PET/CT ve BMB yapıldı. Kemik iliği biyopsisi, kemik iliği tutulumunu değerlendirmede standart referans olarak kabul edildi. Bulgular: Hastaların 61’inde (38%) HL ve 100’ünde (62%) aNHL vardı. Değerlendirilen 126 hastada (78%) (52 HL, 74 aNHL) PET/CT ve BMB arasında uyumlu sonuçlar olduğu görüldü. Bu hastalardan 20’sinde kemik iliği tutulumu bakımından PET/CT ve BMB sonuçları pozitif ve 106 hastanın PET/CT ve BMB negatif bulundu. Diğer taraftan 35 hastada (9 HL, 26 aNHL) uyumsuzluk vardı. Bu hastaların da 16’sında BMB pozitif iken PET/CT sonuçları negatif bulundu. Geri kalan 19 hastada BMB negatif ve PET/CT sonuçları pozitif saptandı. Sonuç: Biz aNHL ve HL hastalarını değerlendirmede tek başına yeterli olmamasına rağmen, PET/CT nin kemik iliği infiltrasyonunu belirlemede etkili olduğunu gözlemledik. Lenfomalı hastalarda kemik iliği infiltrasyonunu belirlemede; BMB ve PET/CT birbirinin tamamlayıcısı olarak düşünülmelidir. Fokal tutulumdan şüphelenildiğinde, BMB ve PET/CT’nin birlikte yapılması hastalığın evrelemesinde daha doğru sonuçlar verebilir.
Atalay, Altay; Gökahmetoğlu, Selma; Durmaz, Süleyman; Kandemir, Idris; Sağlam, Derya; Kaynar, Leylagül; Eser, Bülent; Cetin, Mustafa; Kılıç, Hüseyin
Amaç: Bu çalışmada, 2009-2010 yılları arasında allojenik kök hücre transplantasyonu (AKHT) yapılan hastalarda transplantasyon sonrası EBV ve parvovirus B19 DNA araştırılması amaçlandı. Gereç ve Yöntemler: Bu çalışmaya Erciyes Üniversitesi Tıp Fakültesi İç Hastalıkları Anabilim Dalı Hematoloji-Onkoloji Bilim Dalı’nda Nisan 2009-Kasım 2010 tarihleri arasında AKHT yapılmış 45 erişkin hasta dahil edildi. Hastaların transplantasyon sonrası 1-6. aylar arasında alınan toplam 135 plazma örneğinde EBV ve parvovirus B19 DNA varlığı gerçek zamanlı PCR yöntemi ile araştırıldı. Hastalara ait transplantasyon öncesi EBV ve parvovirus B19 serolojik göstergeleri hasta dosyalarından temin edildi. Bulgular: AKHT öncesi serolojik göstergelerde, 45 hastanın 32’sinde (%71,1) EBNA-1 IgG (+), VCA IgM (-) ve VCA IgG (+) idi. İki hastada (%4,45) EBNA-1 IgG (+), VCA IgM (-) ve VCA IgG (-), bir hastada (%2,2) EBNA-1 IgG (-), VCA IgM (-) ve VCA IgG (+) ve 2 (%4,45) hastada tüm serolojik göstergeler negatifti. Transplantasyon sonrası düşük EBV DNA pozitifliği (<600 kopya/mL) 4 (%8,9) hastada saptandı, bu hastaların hepsinde VCA IgM negatif, VCA IgG pozitif bulundu. Düşük viral yüke rağmen bu hastalarda EBV ilişkili semptom görülmemiş ve PTLD gelişmemiştir. Kırk beş hastanın 44’ünde (%97,7) parvovirus B19 IgM negatif, IgG pozitif iken sadece bir hastada (%2,3) parvovirus B19 IgM pozitif, IgG negatifti. Kırk beş hastadan elde edilen örneklerin hiçbirinde parvovirus B19 DNA saptanmadı. Sonuç: Bu çalışmada AKHT hastalarında EBV ve parvovirus B19 DNA araştırıldı. Hastaların hiçbirinde PTLD gelişmezken parvovirus B19 DNA pozitifliği de saptanmadı. Ancak bu konunun aydınlatılmasında daha geniş hasta serileri ile yapılan, prospektif, çok merkezli ileri çalışmalara ihtiyaç vardır.
Erdoğan, Yurdanur; Özyürek, Berna Akıncı; Özmen, Özlem; Yılmaz Demirci, Nilgün; Duyar, Sezgi Şahin; Dadalı, Yeliz; Demirağ, Funda; Karakaya, Jale
Amaç: Organize pnömoni (OP), respiratuvar bronşiyoller, alveoler kanallar ve alveollerde fibroblastik tıkaçların oluşturduğu polipoid yapılarla karakterize histopatolojik bir durumdur. Radyolojik olarak OP’nin tipik, soliter-fokal ve infiltratif olmak üzere 3 karakteristik görünümü vardır. Pozitron Emisyon Tomografi-Bilgisayarlı Tomografisi’de (PET-BT) yüksek FDG tutulumu malin hastalıklarda olduğu gibi OP gibi benin hastalıklarda da görülebilir. Bu çalışmada maliniteyi taklit eden OP’li olgulardaki PET-BT bulgularını değerlendirmeyi amaçladık. Yöntem: Çalışmamızda 2009-2013 yılları arasında Atatürk Göğüs Hastalıkları ve Göğüs Cerrahisi Eğitim Araştırma Hastanesine dış merkezlerden akciğer grafisi veya toraks bilgisayarlı tomografisinde akciğer malinitesinden şüphelenilerek, ileri tetkik ve tedavi amaçlı yönlendirilen ve malinite ön tanısı ile PET-BT çekilen 50 OP’li olgu dahil edildi. Retrospektif olarak radyolojik ve klinik özellikleri kayıt edildi. Bulgular: Çalışmaya dahil edilen olguların yaş ortalaması 58,2 idi. Yüzde 96’sını (48) erkek hastalar oluşturmaktaydı. Radyolojik olarak PET- BT’de 27 (%54) olguda fokal, 10 (%20) olguda hava bronkogramı içeren konsolidasyon (tipik), 1 (%2) olguda infiltratif ve 12 (%24) olguda da diğer görünümler (multiple nodüller, multiple kaviter lezyonlar) saptandı. PET- BT’de lezyonların maksimum standart tutulum değerlerinin (SUVmax) ortalaması 6,5 olarak hesaplandı. Çalışma grubunun %76’sında en az bir istasyonda mediastinal lenf nodu tutulumu saptandı. Lenf nodlarının ortalama SUVmax değeri 3,27 idi. Sonuç: Organize pnömoniler PET-BT’de yanlış pozitif sonuçlara yol açabilir. Ancak PET-BT maliniteden şüphe ediliyorsa yapılması gereken invaziv yöntemlere yol gösterici olarak kullanılabilir.
Terzi, Yunus Kasım; Bulakbaşı Balcı, Tuğçe; Boğa, Can; Koç, Zafer; Yılmaz Çelik, Zerrin; Özdoğu, Hakan; Karakuş, Sema; Şahin, Feride İffet
Amaç: Hemokromatozis, demir birikiminin önemli nedenlerinden biri olan otozomal resesif bir hastalıktır. Orak hücreli anemi, hemoglobin genindeki homozigot mutasyon sonucu ortaya çıkan bir hemoglobinopatidir. Eritrosit transfüzyonu, bu hastalığın tedavisinde sıklıkla kullanılmaktadır. Transfüzyonun yarattığı demir yükü diğer hemoglobinopatilerde olduğu gibi orak hücreli anemi hastalarının mortalite ve morbiditesinde önem kazanmaktadır. Bu çalışmada hemokromatozis geni (HFE) p.H63D ve p.C282Y mutasyonlarının, homozigot hemoglobin S mutasyonu taşıyan orak hücreli anemi hastalarında, kalp ve karaciğerde transfüzyonla ilişkili demir yüklenmesine olan etkisi araştırılmıştır. Gereç ve Yöntemler: Bu çalışma, homozigot hemoglobin S mutasyonu olan hastalarda 2008-2013 yıllarını kapsayan prospektif, tek merkezli kesitsel bir çalışmadır. Hastalar şelasyon tedavisi alan (n=31) ve almayan (n=13) olarak iki gruba ayrıldı. Hastalarda direk ve endirekt demir yükü sırasıyla manyetik rezonans görüntüleme ve biyokimyasal olarak analiz edildi. HFE geni mutasyon analizi polimeraz zincir reaksiyonu-restriksiyon fragment uzunluk polimorfizmi yöntemleri ile gerçekleştirildi. İstatistik analizi Independent samples t-testi uygulanarak gerçekleştirildi. Bulgular: p.H63D mutasyonu grup A’da 10 hastada (%32,3), grup B’de ise sadece 1 (%7,7) hastada saptandı. Demir birikimi açısından gruplar karşılaştırıldığında karaciğerde demir birikiminin grup B’de istatistiksel olarak anlamlı derecede yüksek olduğu görülmüştür (p<0,05). Grup A’da, mutasyonu olan bireylerde olmayanlara göre karaciğerdeki demir birikiminin istatistiksel olarak anlamlı derecede yüksek olduğu görülmüştür (p=0,05). Sonuç: Bu çalışmanın sonucu HFE genindeki mutasyonların, orak hücreli anemi hastalarında karaciğerde demir birikimi üzerinde etkili olduğunu göstermektedir.