Arsenic fractionation in agricultural acid soils from NW Spain using a sequential extraction procedure

Arsenic fractionation has been studied in nine vineyard soils from a wine-producing area in Galicia (NW Spain) characterized by an unusually high As content. Total As concentrations are 7 to 10 times higher the maximum values allowed by the legislation, reaching maximum value of 200 mg kg(-1). The study of As fractionation revealed that those fractions showing strong correlations to crystalline Fe and Al hydrous oxides (r>0.69, p<0.01 and r>0.71, p<0.01 respectively) represented, on average, higher than the 80% of total As. The low levels of mobile and potentially toxic As fractions (<4% of total As) suggest that its toxicity is partially minimized in these soils, although the modifications induced by soil management could promote an increase of As availability.     

Metal phase associations in soils from an urban watershed, Honolulu, Hawaii

Soils of Manoa watershed, Hawaii, have received varying inputs of anthropogenic trace metals, with roadside soils primarily influenced by automobile contributions. A four-stage sequential extraction procedure was used to fractionate 13 topsoil (0-2.5 cm) and 13 subsoil (7.5-10.0 cm) samples into: (i) an adsorbed, exchangeable and carbonate (AEC) phase; (ii) a reducible phase; (iii) an oxidizable phase; and (iv) a residual phase. Phases (i)-(iii) were considered 'labile', with the residual fraction 'non-labile' under normal circumstances. An examination of eight elements (Al, Co, Cu, Fe, Mn, Ni, Pb and Zn) indicated that Pb was the trace metal most impacted by anthropogenic inputs. Roadside soil Pb enrichment was apparent with data from a 0.5 M HCI leach exhibiting a maximum concentration of 1000 mg/kg compared with a median background value of 12 mg/kg. Sequential extraction results indicated the following order with respect to phase dominance for Pb: reducible > residual > oxidizable > AEC. The identification of the reducible phase as the primary pool of available Pb supports previous work from temperate roadside soil environments. The reducible phase is characterized by hydrous Fe and Mn oxides and mobilization of fixed elements can occur with decreases in pH and redox potential. Iron was the least labile of the elements examined with only 5-6% of total Fe removed by the first three steps of the extraction procedure. Lead had the highest labile percentage with average values between 74 and 81%. Therefore, results from this study support earlier research in this watershed which identified Pb as the primary trace metal of concern from a contamination perspective.     

Analysis of composition, distribution and origin of hexachlorocyclohexane residues in agricultural soils from NW Spain

Concentrations of the isomers of the organochlorine pesticide hexachlorocyclohexane (HCH) were determined in 252 surface soil samples collected within a sampling network covering agricultural areas in Galicia (NW Spain). The concentration of total HCH (sum of α + β + γ + δ) ranged between 4 and 2305 ng g⁻¹ (dry weight), with the α-HCH and γ-HCH isomers predominating (< 1-1404 ng g⁻¹ and < 1-569 ng g⁻¹, respectively). The distribution of the pesticide residues was very heterogeneous, with the largest concentrations present in one of the studied areas (the province of A Coruña). The distribution of HCH was not found to be related to any soil property (organic matter, pH, clays, and metals). Multivariate statistical analysis of the data revealed that three populations of samples with a defined composition of HCH, can be related to the source of HCH: technical HCH (α/γ > 3), lindane (99% γ-HCH), or both. The existence of a third population consisting almost exclusively of α-HCH suggests that background contamination of anthropogenic origin dates from several decades ago. The detailed analysis of these populations enabled the possible temporal scale of the application of these pesticides to be deduced.     

Pollution of soils by the toxic spill of a pyrite mine (Aznalcollar, Spain)

On 25 April 1998 the retention walls broke open in a pond containing the residues from a pyrite mine of Aznalcollar (southern Spain), spilling some 45 x 10(5) m3 of polluted water and toxic tailings into the Agrio and Guadiamar River basin, affecting some 55 km2. On 5 May, seven sectors in the affected area were studied, analysing tailings, polluted water, and contaminated as well as uncontaminated soils. The principal pollutants were: Zn, Pb, Cu, As, Sb, Bi, Cd and Tl. The range of total contamination of each element was extremely broad, as penetration of the tailings depended on the soil characteristics. Most of the Cu, Zn and Cd penetrated the soil in the solution phase of the spill, while the other elements penetrated mostly as part of the solid phase. Zn exceeded the maximum concentrations permitted by the international community in four of the seven sectors studied, As in three, and the other elements only in one sector. Drying and consequent aeration of the tailings rapidly oxidized sulphides to sulphates, lowered the pH and solubilized the pollutants. Therefore, future rains could aggravate the pollution problem, if the tailings are not quickly removed.     

Metal redistribution by surface casting of four earthworm species in sandy and loamy clay soils

Bioturbation of metal contaminated soils contributes considerably to redistribution and surfacing of contaminated soil from deeper layers. To experimentally measure the contribution of Allolobophora chlorotica, Aporrectodea caliginosa, Lumbricus rubellus and L. terrestris to soil surface casting, a time-course experiment was performed under laboratory conditions. Earthworms were incubated in perspex columns filled with sandy soil (2% organic matter, 2.9% clay) or loamy clay soil (15% organic matter, 20% clay), and surface casts were collected after up to 80 days. On the sandy soil, A. caliginosa and L. rubellus brought approximately 7.1-16 g dry wt. casts/g fresh wt. earthworm to the surface, which is significantly more than A. chlorotica and L. terrestris (2.5-5.0 g dry wt./g fresh wt.). A. caliginosa was the only species that produced significantly more surface casts in the sandy soil than in the loamy clay soil. In the loamy clay soil, no differences in biomass-corrected casting rates were found among the species. Surface casting rates tended to decrease after 20 days. Considering the densities of the different species in a Dutch floodplain area Afferdensche and Deestsche Waarden, surface cast production is estimated to amount to 2.0 kg dry soil/m² after 80 days, which could be extrapolated to 2.7-9.1 kg/m² per year. These amounts correspond to a surface deposition of a layer of approximately 1.9-6.5 mm/year, which is of the same order or even slightly higher than the sedimentation rate and much higher than the amount of soil brought to the soil surface by bioturbating small mammals.     

Comparison of the feasibility of three extraction procedures for trace metal partitioning in sediments from south-west Spain

The feasibility of three sequential extraction schemes (a modification of the Tessier procedure, the scheme proposed by Meguellati and the protocol designed by BCR (now called the Standards, Measurements and Testing Programme, M&T) have been compared to study the distribution of As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb and Zn in sediment samples. The comparison has been performed by analyzing Certified Reference Material (CRM-601), a test material (S-12) and seven sediments from the Odiel Marshes Natural Park (located at the Atlantic coast of southern Spain). Samples were classified as sandy (with low iron oxide and organic matter contents) and clay-silty (with high iron oxide and organic matter contents) sediments. A higher metal mobility, especially under reducing conditions, was more properly assessed using the modified Tessier scheme compared to both the BCR and Meguellati procedures, these two later presenting comparative results for the reducible and residual phases. Significant Hg losses were found using the BCR procedure but the quantification of the acid phase for Cd, Cr and Ni was more reliable than that obtained with the modified Tessier and Meguellati schemes.     

Distribution and mobility of mercury in soils from an old mining area in Mieres, Asturias (Spain)

Mercury content in soils near abandoned mine wastes in the mercury mining area of Mieres (Asturias, Spain) is highly elevated as a result of the long period of mining and abundant Hg production. In this work, an evaluation of Hg concentration, distribution, and mobility in three soil samples from the immediate vicinity of a chimney used for vapour evacuation during pyrometallurgical treatment of the ore was carried out. For that purpose, total Hg contents were determined for the original samples and their grain-size subsamples. The study of mercury mobility in the original samples and in the different particle-size subsamples was made by the application of a sequential extraction method. Results showed that Hg concentration in soils decreases directly with the distance from the chimney and the dispersion of Hg is not influenced by the topographic height of the site tested. The sample collected in the base of the chimney exhibited appreciable amounts of mobile Hg. In general, a higher Hg concentration was found for the finest particle-size subsamples. Hg mobility was found to be higher for quite developed soils. The sample collected downstream from the chimney showed a significant Hg mobile content as a result of a more intensive weathering. An increase of Hg mobility at decreasing particle size was found in all three analysed samples.     

Suitability of the OCDE tests to estimate contamination with 2,4-dichlorophenol of soils from Galicia (NW Spain)

The objective of the present study was to verify whether the generic reference levels (GRL) for soils contaminated with 2,4-dichlorophenol (2,4 DCP), established by Spanish legislation and published in the Real Decreto 9/2005, are accurate for Galician soils. For this, the surface horizons of seven soils under different types of land use were experimentally contaminated with different doses (between 0 and 10,000 times the GRL) of 2,4 DCP, and were then were subject to OECD toxicity test numbers 208 (root emergence and elongation) and 216 (soil nitrogen mineralization). The results obtained for the nitrogen mineralization test were difficult to interpret because they varied among soils, whereas the results of the root germination and elongation test were more coherent -- the values decreased with increasing doses of contaminant added to the soil. The results suggest that the root elongation test reflects the effect of this contaminant more clearly than the soil nitrogen mineralization test. Nevertheless, considering that in the lowest quality soils (i.e. agricultural soils containing a very low level of organic matter) contaminant doses of up to 1000 times the GRL did not affect root germination and elongation, it is clear that the GRL indicated in the relevant legislation are very low for the soils under study and that the threshold should be established taking into account the soil characteristics.     

Compaction of water-saturated soils by blasts from elongated charges

Experience with compaction of bases consisting of water-saturated cohesionless and cohesive soils by blasts from vertical elongated charges in Poland and many other countries is described. Examples of this method, which confirm its effectiveness and economy, are given.Translated from Osnovaniya, Fundamenty i Mekhanika Gruntov, No. 4, pp. 24–26, July–August, 1992.     

雌激素受体拮抗剂对泌乳素腺瘤GH_3细胞增殖的影响

目的:探讨雌激素受体拮抗剂对泌乳素腺瘤细胞增殖的影响。方法:在同样去激素培养的条件下添加不同浓度雌激素和雌激素受体拮抗剂,应用MTT法检测其对GH_3细胞增殖的影响。结果:不同浓度的OHTam对GH_3细胞有明显的抑制作用,并且与剂量呈正相关,10~(-11) mol/L即有抑制作用,10~(-6) mol/L抑制作用达到最大。E_2可显著的刺激GH_3细胞增殖,10~(-12)mol/L即有促进增殖作用,10~(-9) mol/L作用达到最大,而后随着浓度的升高增殖作用反而逐渐减弱。结论:雌激素受体拮抗剂能显著抑制泌乳素腺瘤细胞的生长,理论上可以用于泌乳素腺瘤的药物治疗。     

Mn and Ni contents in soils of a qualified denomination of origin region: Rioja D.O.Ca,Spain

The distribution of Mn and Ni in soils of one of the most famous winegrowing regions of Spain, Rioja D.O.Ca (Denomination of origin, Spain's top category), was studied in detail according to its geographical location. There were background concentrations of 288.81 mg kg^?1 total Mn in the surface horizon and 296.06 mg kg^?1 in the subsoil; and a total Ni content of 17.89 mg kg^?1 in the surface horizon and 24.76 mg kg^?1 in the subsoil. The amounts of Mn bio- or phytoavailable were 5.28 mg kg^?1 in the upper horizon and 4.70 mg kg^?1 in the subsurface horizon; and for Ni bio- or phytoavailable, the amounts were 0.14 mg kg^?1 in the upper horizon and 0.13 mg kg^?1 in the deeper horizon. Spatial distribution patterns were established using GIS contour maps for the two elements, showing significant variations within and between the sites. The local contamination is generally associated with the quantities that are added to the soil or water from man-made sources such as industrial discharge and volatile emissions, sewage sludge, livestock wastes and other wastes.     

Experimental and modelling study of plutonium uptake by suspended matter in aquatic environments from southern Spain.

Kinetic transfer coefficients are important parameters to understand and reliably model the behaviour of non-conservative radionuclides in aquatic environments. This report pertains to a series of five radiotracer experiments on Pu uptake in natural aqueous suspensions of unfiltered waters from three aquatic systems in the south of Spain (Gergal reservoir, the Guadalquivir river, and the estuary of the Tinto river). The experimental procedure ensured the simulation of environmental conditions. Pu activity was measured by a liquid scintillation technique. The uptake curves, covering a period up to one week, are discussed with respect to numerical uptake kinetics models. The data suggest that in our experimental setting the main pathways for Pu uptake consist of two parallel and reversible reactions followed by a consecutive non-reversible reaction. Kinetic transfer coefficients were estimated by a fitting procedure and a comparative study was followed.     

Study of the copper distribution in contaminated soils of hop fields by single and sequential extraction procedures

Hop growing in Bavaria requires the use of copper containing fungicides against mildew, which results in an accumulation of copper in the upper soils to concentrations of up to approximately 450 mg kg(-1). The naturally occurring concentration of copper is approximately 10-15 times lower. Several single and sequential extractions were performed in parallel to the determination of total copper content after aqua regia digestion. By these means copper mobility and retention, its availability to plants as well as its distribution in soils was assessed. Three agricultural soils and two soils from fallow land have been analysed to elucidate whether the copper distribution changes in relation to agricultural activities and to predict environmental risks due to the high copper concentrations. This work also focuses on the difficulties arising from different results when using single and sequential extraction procedures. EDTA, acetic acid, deionised water, ammonium nitrate and calcium chloride were used as single extractants for the functionally defined speciation. EDTA and acetic acid can be regarded as extractants for the plant-available species, while deionised water, NH4NO3 and CaCl2 only release electrostatically weakly bound metals to estimate the mobile species. The extraction behaviour of copper in these procedures is discussed with respect to the quantities extracted from the contaminated and non-contaminated soils. The studies indicate that no vertical copper translocation is observed in the ground, but the main amounts are highly available to plants. Sequential extraction procedures were used for operationally defined speciation, quantifying copper in specific soil phases. The 'five-step extraction scheme' first applied, suggested by the Standard Measurement and Testing Programme of the European Community, overestimated the amounts of copper bound to the residual phase. This was mainly due to the non-specific nature of the reagents for the organic/sulfidic and crystalline iron oxide fraction. A second reason could be the fact that this scheme was developed for sediment and not for soil analysis. Therefore, the sequential extraction has been applied using an adapted method of Zeien and Bruemmer, using different extractants for the two phases. The copper distribution was different, showing that approximately 40-50% of the total copper was bound to the organic fraction and approximately 15-30% could be extracted with the iron oxides. The amounts in the residual fraction were much lower. After comparing the results of the different extraction procedures the environmental behaviour of copper and its risks for plants, micro-organisms and groundwater is discussed in brief.     

Mercury release from deforested soils triggered by base cation enrichment

The Brazilian Amazon has experienced considerable colonization in the last few decades. Family agriculture based on slash-and-burn enables millions of people to live in that region. However, the poor nutrient content of most Amazonian soils requires cation-rich ashes from the burning of the vegetation biomass for cultivation to be successful, which leads to forest ecosystem degradation, soil erosion and mercury contamination. While recent studies have suggested that mercury present in soils was transferred towards rivers upon deforestation, little is known about the dynamics between agricultural land-use and mercury leaching. In this context, the present study proposes an explanation that illustrates how agricultural land-use triggers mercury loss from soils. This explanation lies in the competition between base cations and mercury in soils which are characterized by a low adsorption capacity. Since these soils are naturally very poor in base cations, the burning of the forest biomass suddenly brings high quantities of base cations to soils, destabilizing the previous equilibrium amongst cations. Base cation enrichment triggers mobility in soil cations, rapidly dislocating mercury atoms. This conclusion comes from principal component analyses illustrating that agricultural land-use was associated with base cation enrichment and mercury depletion. The overall conclusions highlight a pernicious cycle: while soil nutrient enrichment actually occurs through biomass burning, although on a temporary basis, there is a loss in Hg content, which is leached to rivers, entering the aquatic chain, and posing a potential health threat to local populations. Data presented here reflects three decades of deforestation activities, but little is known about the long-term impact of such a disequilibrium. These findings may have repercussions on our understanding of the complex dynamics of deforestation and agriculture worldwide.     

Metal and sediment ingestion by dabbling ducks.

The chemical analysis of intestinal digesta from hunter-killed carcasses or of wildlife scat is a promising means of estimating the exposure of wildlife to those environmental contaminants that, like lead, are poorly absorbed in the digestive tract. When evaluating contaminants at a site, biologists may find the results of this non-destructive approach more straightforward to interpret in terms of exposure to wildlife than would be analyses of soils, sediments, water, or wildlife tissues. To illustrate the approach, we collected digesta from 47 waterfowl shot by hunters at Prime Hook National Wildlife Refuge, in Delaware, USA. The waterfowl digesta contained an average of approximately 2.4% sediment, estimated from the Al concentrations in the digesta, a marker for sediment. Al concentrations were significantly correlated with concentrations of Cr (Spearman's rank correlation coefficient, r = 0.57), V (r = 0.70), Ni (r = 0.31), and Pb (r = 0.55), and we concluded that these metals were ingested mainly with sediment. American widgeon (Anas americana) ingested sediment at a rate of about four times that of three other species of dabbling ducks (Anas crecca, A. acuta, A. rubripes) and had several times the exposure to the sediment-associated metals. The digesta of one American black duck contained a high concentration of lead (70 mg/kg, dry wt.), presumably from lead shot, but none of the other samples had notably elevated metal concentrations. We suggest that scat and digesta be analyzed more widely by biologists and resource managers seeking a simple, inexpensive assessment of contaminants in local wildlife habitat.     

超声波辅助醇提取鸡血藤总黄酮工艺研究

目的筛选提取鸡血藤总黄酮的最佳工艺条件。方法采用正交试验对提取工艺进行优化;分别以干浸膏得率和单位浸膏中总黄酮含量为指标,对提取工艺进行评价。结果最佳提取工艺条件为8倍量50%乙醇,超声波功率为100 W,提取时间为1.5 h,提取温度为80℃。结论该提取方法稳定、可行,为优化鸡血藤总黄酮的最佳提取工艺提供了参考依据。     

离子液体提取茶叶中咖啡因的工艺研究

以离子液体[HSO3-pmim]+[HSO4]-为提取剂,以咖啡因的产量为评价指标,从茶叶中提取咖啡因。通过单因素实验考察了料液比、提取时间、提取温度、离子液体浓度对咖啡因产量的影响。实验结果表明,料液比、提取时间、提取温度、离子液体浓度对咖啡因的产量有较大影响,当料液比为1∶25,提取温度为95℃,提取时间为180 min,离子液体浓度为80%时,咖啡因产量最高为108.6 mg。该方法简便,易于操作,对环境无污染,同时产品产量高、纯度好。     

Protecting the bed soils of foundations from damaging wetting by acids

The properties of different lithological types of soils are investigated prior to and after exposure to concentrated thermophosphoric acid within the bounds of a plant run by the Slavyansk Production Union “Khimprom.” The possibility of reducing mineralization of the acid-containing rocks and ground water by flushing them and neutralization with various solutions is studied. A working design of a drainage system, which provides for sanitation of ecological conditions and improves the performance of foundation structures, is developed. Translated from Osnovaniya, Fundamenty i Mekhanika Gruntov, No. 4, pp. 14–17, July–August, 1995.     

Evaluation of dioxin contamination in sewage sludge discharges on coastal sediments from Catalonia, Spain.

The fate of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in sewage sludges after discharge into the sea was investigated. Sediment samples were analysed at a sewage sludge disposal site as well as in the surrounding areas. Moreover, eight sediment samples from two rivers in Catalonia and three sediment samples from Catalonian Coast were analysed to determine the background levels of contamination. Total international toxicity equivalent (I-TEQ) values for these sediments ranged from 0.42 to 8.01 pg g, with a mean value of 4.15 pg/g and a median value of 3.69 pg/g. However, the I-TEQ values of sludge-treated areas were higher: 57.04 pg/g at the dumping site, and within a range of 13.42-47.76 pg/g near this site. Thus, European sediment quality objectives were exceeded. The higher concentrations coincided with changes in the ratio between PCDD and PCDF levels, suggesting the influence of the sewage sludge on coastal sediments.