Xabier Pontevedra-Pombal

Four Thousand Years of Atmospheric Pb, Cd and Zn Deposition Recorded by the Ombrotrophic Peat Bog of Penido Vello (Northwestern Spain)

The Northwestern Iberian Peninsula is a mid-latitude oceanic region with areas where different types of bogs are frequent or abundant. The ombrotrophic nature of some bogs make them suitable for the study of accumulation patterns of heavy metals. One of these bogs, Penido Vello, was sampled to a depth of 2.5 m and analyzed in detail for its physico-chemical properties and Pb, Zn and Cd concentrations. Ash and organic carbon content, Ca/Mg molar ratios and a number of other characteristics support an ombrotrophic interpretation of the core. Concentrations of Pb, Zn and Cd were measured, showing important variations in the core. While Zn and Cd are concentrated mainly in the upper sections of the core with minor changes with depth, the Pb profile shows significant peaks in the deeper layers suggesting pre-industrial atmospheric pollution. Enrichment factors (EFs) calculated by normalising to Al correlate well with those calculated by normalising to Ti. Maximum EFs are 33, 56 and 52 for Pb, Zn and Cd respectively. While for Pb these values are comparable to those obtained by other authors, maximum Zn EFs are greater than those mentioned in the literature and may be attributed to the emissions of a nearby coal-burning power plant. At least for Pb the accumulation pattern suggests that atmospheric pollution can be dated back some 2800 years, and that pollution increased steadily since the Iron Age to reach considerably elevated levels, up to 5 times the ‘background’, during the Roman Empire. Changes in Pb emissions through time are in good accord with the prehistorical and historical record of the Iberian Peninsula.

Mercury accumulation in upland acid forest ecosystems nearby a coal-fired power-plant in Southwest Europe (Galicia, NW Spain)

This study was carried out to determine total Hg concentrations (HgT) in acid soils and main plant species in forest ecosystems located in the river Sor catchment, which is located 20 km to the NE of the biggest coal-fired power-plant in southwestern Europe (Galicia, NW Spain). Mercury enrichment factors and Hg inventories were also determined in the soils, which were regularly sampled between 1992 and 2001. The presence of elemental Hg was estimated by simple thermal desorption at 105 degrees C. The highest HgT concentrations occurred in upper soil layers (O and A horizons) with values up to 300 ng g(-1). HgT decreased with depth, achieving the lowest values in the bottommost horizons (i.e. the soil parent material, <6 ng g(-1)), except in podzolic soils. A similar trend occurred for Hg enrichment factors (HgEF) which showed values from 40 to 76 in topsoils. Upper soil mineral horizons (A or AB) made the largest contribution (>50%) to the HgT inventory despite showing lower concentrations than the organic horizons. The role of vegetation in capturing atmospheric Hg and subsequent deposition to soil agrees with the sequence of HgT in plant material: wood<living leaves/needles<litterfall. The thermal desorption test revealed that almost all Hg is matrix-bound. Multiple regression analysis indicated that total organic carbon and Fe extracted in Na-pyrophosphate explains 87% of the variance of HgT concentrations, suggesting that organic matter (total amount and the presence of metal-humus compounds) plays a key role in Hg accumulation in the studied acid soils.

Comparative performance of extraction strategies for polycyclic aromatic hydrocarbons in peats.

The assessment of historical trends in atmospheric deposition of organic contaminants by using peat samples has been reported on several occasions because these samples represent an almost ideal medium for recording temporal changes in organic contaminant deposition rates. The determination of polycyclic aromatic hydrocarbons (PAHs) in peat samples is complicated due to the high content of organic matter in peat, which affects both extraction efficiency and analytical quality. A rapid and simple method is proposed for the determination of 10 US Environmental Protection Agency indicator PAHs in complex matrices such as peat. This article reviews and addresses the most relevant analytical methods for determining PAHs in peat. We discuss and critically evaluate three different extraction procedures, such as ultrasound-assisted solvent extraction (UASE), shaking and pressurized liquid extraction (PLE). Clean-up of extracts was performed by solid-phase extraction using silica cartridges. Detection of the selected PAHs was carried out by high-performance liquid chromatography coupled with fluorescence detection for determination. Optimization of the variables affecting extraction by the selected extraction techniques was conducted, concluding that the UASE extraction method using hexane:dichloromethane (80:20) as extractant was robust enough to determine the selected PAHs in peat samples with estimated quantification limits between 0.050 and 3.5 microg/kg depending on the PAH. UASE did not demand sophisticated equipment and long extraction times. PLE involved sophisticated equipment and showed important variations in the results. The method proposed was applied to the determination of PAHs in peat samples from Xistral Mountains (Galicia, Spain).

Pre-industrial accumulation of anthropogenic polycyclic aromatic hydrocarbons found in a blanket bog of the Iberian Peninsula.

Studies on the temporal deposition of polycyclic aromatic hydrocarbons (PAHs) in peatlands are scarce, and none have been carried out in the Iberian Peninsula. To address this gap, ten PAHs were determined in a short peat core (spanning the last 1000 years) sampled in NW Iberian Peninsula, by HPLC-fluorescence. Fluoranthene, pyrene, benzo[b]fluoranthene and indeno[1,2,3-cd]pyrene predominated in the upper layers (10 cm), whereas fluoranthene and pyrene were the most abundant in the lower layers (40 cm), which showed an absence of high molecular weight PAHs (benzo[ghi]perylene and Indeno[1,2,3-cd]pyrene). Although increased PAH contents have been detected since 1700 A.D., coinciding with the beginning of the Metallurgical and Industrial Revolution, high levels of fluoranthene and pyrene were present in peat samples dating back to the 12th century A.D. The results suggest that changes in sources, type of emission (global or local) and transport could be responsible for the different PAH content and composition of the peat core. These changes are consistent with the history of the use of natural resources in the NW of the Iberian Peninsula.

Molecular chemistry by pyrolysis-GC/MS of selected samples of the Penido Vello peat deposit, Galicia, N.W. Spain

Publisher Summary Molecular chemistry reveals significant differences between extracted and non-extractable (residue) peat. In the extracts, lignin and other aromatic fragments, nitrogen-containing moieties are more abundant whereas aliphatics, methyl ketones and lipids are more abundant in the non-extractable fraction. This is not astonishing, since partly oxidized lignin and proteins are hydrophilic and extractable with NaOH, whereas for the extraction of lipids one needs organic solvents. Short-chain straight aliphatics are more abundant in the extractable fraction, and there appears to be a regular decay series of alkanes and alkenes from n -C 28, 28:1 to n -C 10 . One branched alkane that is predominantly present in the extractable fraction is possibly of microbial origin. Some polysaccharide moieties are specifically associated with the extractable fraction and some with the residues. This probably reflects a predominantly microbial origin for the first and predominantly plant-derived for the second, because the plant-derived polysaccharides may still be present in larger molecular units.

Atmospheric pollutants in fog and rain events at the northwestern mountains of the Iberian Peninsula

Atmospheric polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) are persistent organic pollutants (POPs) and exist in gas and particle phases, as well as dissolved or suspended in precipitation (fog or rain). While the hydrosphere is the main reservoir for PAHs, the atmosphere serves as the primary route for global transport of PCBs. In this study, fog and rain samples were collected during fourteen events from September 2011 to April 2012 in the Xistral Mountains, a remote range in the NW Iberian Peninsula. PAH compounds [especially of low molecular weight (LMW)] were universally found, but mainly in the fog-water samples. The total PAH concentration in fog-water ranged from non-detected to 216 ng·L(-1) (mean of 45 ng·L(-1)), and was much higher in fall than in winter. Total PAH levels in the rain and fog events varied from non-detected to 1272 and 33 ng·L(-1) for, respectively, LMW and high molecular weight (HMW) PAHs. Diagnostic ratio analysis (LMW PAHs/HMW PAHs) suggested that petroleum combustion was the dominant contributor to PAHs in the area. Total PCB levels in the rain and fog events varied from non-detected to 305 and 91 ng·L(-1) for, respectively, PCBs with 2-3 Cl atoms and 5-10 Cl atoms. PCBs, especially those with 5-10 Cl atoms, were found linked to rain events. The occurrence of the most volatile PCBs, PCBs with 2-3 Cl atoms, is related to wind transport from far away sources, whereas the occurrence of PCBs with 5-10 Cl atoms seems to be related with the increase of its deposition during rainfall at the end of summer and fall. The movement of this fraction of PCBs is facilitated by its binding to air-suspended particles, whose concentrations usually show an increase as the result of a prolonged period of drought in summer.

Chapter 4 Mountain mires from Galicia (NW Spain)

Publisher Summary Galician mires have formed during the Late Quaternary in three main phases. During the Preboreal and the Boreal (11,000–8500 years ago) minerogenic mires were formed, in the mid Atlantic (7800–7100 years ago) both minerogenic and ombrogenic mires developed and between the mid Atlantic and the beginning of the sub-Boreal (6000–2000 years ago) an expansion of ombrogenic mires and a stabilization of ecologic conditions of the minerogenic ones took place. Strong oceanic influence, high precipitation, and wide geomorphologic heterogeneity, linked to Quaternary evolution, allowed the development of more than 10,000 ha of mires ecosystems in Galicia (NW Spain). The peculiarities associated to their formation and evolution makes these wetlands important in Europe, some having developed at extreme geographic locations.

Total mercury distribution among soil aggregate size fractions in a temperate forest podzol

This study determined the distribution of total Hg (HgT) among aggregate size fractions in the A, E, Bh and Bs horizons of a representative temperate forest podzol. The aggregate distribution was dominated by the coarse sand size fraction (average of 55%) followed by fine sand (29%), fine silt (10%), coarse silt (4%) and clay (2%). In general, HgT mean values increased as the aggregate size become smaller: clay (170 ng g-1) > fine silt (130 ng g-1) > coarse silt (80 ng g-1) > fine sand (32 ng g-1) > coarse sand (14 ng g-1). Total Hg enrichment in clay-sized aggregates ranged from 2 to 11 times higher than the values shown by the bulk soil ( 50% of HgT in Bh and Bs horizons. The potential ecological risk index (PERIHg) increased as the aggregate size decreased, with the highest values in the illuvial horizons (45-903) and lowest in the E horizon (3-363). Heterogeneous distribution of Hg in the soil aggregate size fractions must be considered for Hg determination for purposes such as critical loads, background values or environmental risk indices. In addition, Hg accumulation in finer aggregates could be of concern due to its potential mobility in forest soils, either transferred by leaching to groundwater and freshwaters or mobilized by runoff in surface horizons.