The role of afforestation species as a driver of Hg accumulation in organic horizons of forest soils from a Mediterranean mountain area in SW Europe.

Forest areas are a primary sink of atmospheric mercury (Hg) within terrestrial ecosystems, whereas forest vegetation plays a key role in atmospheric Hg transfer to soil horizons. This study assessed variations in total Hg contents (HgT) and accumulation (HgRes) in the soil organic horizons of a forest area in NE Portugal, where post-wildfire afforestation led to the substitution of the native deciduous species (Quercus pyrenaica) by fast-growing coniferous species (Pseudotsuga menziesii and Pinus nigra). The study also evaluated, for each species, the links between Hg contents and other biophilic elements of soil organic matter (C, N, S) present in organic subhorizons (OL, OF, OH). Mean HgT in the organic horizons of the different tree species follow the sequence: P. nigra (88 µg kg-1) < Q.pyrenaica (101 µg kg-1)

Litterfall Hg deposition to an oak forest soil from southwestern Europe.

Litterfall constitutes one of the main vectors for mercury (Hg) transfer to forested ecosystems, so we studied the deposition of Hg through senescent vegetation (oak leaves, twigs and miscellaneous) in a deciduous forest plot of Southwest Europe dominated by Quercus robur in 2015 and 2016. Total Hg concentrations increased in the following order: bole wood (1.4 µg kg-1) < bark (8.3 µg kg-1) < twigs (12.2 µg kg-1) < miscellaneous (36.0 µg kg-1) < oak leaves (39.3 µg kg-1) < mineral soil (42.4 µg kg-1) < Oi horizons (48.7 µg kg-1) < Oe + Oa horizons (71.6 µg kg-1). Mercury accumulation rates in oak leaves during the growing season were 0.15-0.18 µg kg-1 day-1. Mercury deposition fluxes were 26 and 21 µg m-2 yr-1 for 2015 and 2016, respectively, with oak leaves being the fraction that contributed the most. Mercury determination in litterfall sorted biomass fractions lead to a more accurate estimation of the total annual Hg deposition fluxes through litterfall. Higher Hg content was obtained for organic horizons (average of 60.2 µg kg-1) than for mineral soil (mean of 42.4 µg kg-1), but the soil Hg pool was higher in the latter. The results confirmed the necessity of taking into account the Hg pool in the deeper mineral soil layers as they accumulate substantial quantities of Hg associated to organic C and Al compounds, preventing its mobilization to other compartments of the terrestrial ecosystems.

Experimental data and model prediction of tetracycline adsorption and desorption in agricultural soils.

In this work, tetracycline (TC) adsorption and desorption were studied, and the soil properties that most influenced the process were identified. Batch experiments were carried out on 63 crop soil samples, which showed a wide range of values in their physicochemical characteristics. Adsorption curves fit well to the Freundlich equation, with KF values varying between 901 and 9202 Ln µmol1-n kg-1. Kd values ranged between 53 and 6899 L kg-1 for an initial concentration (Co) of 400 µM, whereas the adsorption capacity (qa) ranged from 8541 to 14,852 µmol kg-1. TC retention on soils was high, with adsorption values always higher than 58%, and desorption values lower than 9%. Bivariate correlations and multiple linear regressions were performed to identify those soil variables having a greater influence on TC adsorption and desorption. The results indicate that organic carbon, clay, exchangeable aluminum, available phosphorus, effective cation exchange capacity content, and pH are the main characteristics affecting TC adsorption and desorption. The models, developed by means of multiple linear regression, gave satisfactory and robust predictions for TC adsorption and desorption, using easily determinable soil characteristics as input.

Pedotransfer functions to estimate the adsorption and desorption of sulfadiazine in agricultural soils.

Batch-type experiments were used to study adsorption-desorption of sulfadiazine in 50 crop soils exposed to antibiotic pollution due to the spreading of animal manure or slurry. Adsorption and desorption curves were linear, and were satisfactorily described using the linear and Freundlich equations. The Freundlich adsorption constant (KF(ad)) showed low values (between 0.4 and 9.0 L1/n µmol1-1/n kg-1), which were similar to those of the adsorption constant for the linear model (Kd(ad), between 0.3 and 12.0 L kg-1). Furthermore, the desorption constant for the linear model (Kd(des)) showed higher values than those of Kd(ad), ranging between 1.6 and 29.3 L kg-1, while the values of the Freundlich desorption constant (KF(des)) ranged from 0.10 to 36.8 L1/n µmol1-1/n kg-1. The percentages of adsorption were very variable, ranging from 10 to 87%. The soil characteristics that most influenced adsorption-desorption were those related to soil organic matter (organic carbon and nitrogen contents), as well as the effective cation exchange capacity, and pH. In addition, statistically robust pedotransfer functions were obtained, allowing prediction of adsorption-desorption behavior for sulfadiazine from readily determinable soil parameters, such as pH or organic carbon content.

Copper and zinc in rhizospheric soil of wild plants growing in long-term acid vineyard soils. Insights on availability and metal remediation.

Total and available Cu and Zn levels were assessed in plant biomass, as well as in two rhizosphere fractions (tightly adhering rhizosphere (TAR), and loosely adhering rhizosphere (LAR)), in wild plants species from vineyard soils. Both TAR and LAR fractions were enriched in total Cu and Zn (1.7 and 1.6 times, respectively), and in available Cu and Zn (2.2 and 19.5 times, respectively), with the former being significantly higher for TAR than for LAR fractions. Mean values for total Cu accumulation in root and aerial biomass of the studied wild plants were 84 and 66 mg kg-1, respectively, being 57 and 79 mg kg-1 for Zn. No correlations were found among metal contents in plant biomass and available Cu and Zn concentrations in the rhizosphere fractions. Translocation factor (TF) values for Zn (range 1.0-3.5) indicate preferential accumulation in the aerial biomass in all the studied wild plants. On the contrary, TF for Cu shows a greater variability, depending on plant species, and ranging from 0.2 to 5.9. Regarding bioaccumulation factor (BAF), ranges were 0.03-0.27 and 0.13-0.58, for Cu and Zn, respectively. Results suggest that D. sanguinalis, P. hieracioides, S. viridis, and T. barbata could be useful for Cu remediation in the studied soils, by means of phytostabilization processes.

Degradation of sulfadiazine, sulfachloropyridazine and sulfamethazine in aqueous media.

Antibiotics discharged to the environment constitute a main concern for which different treatment alternatives are being studied, some of them based on antibiotics removal or inactivation using by-products with adsorbent capacity, or which can act as catalyst for photo-degradation. But a preliminary step is to determine the general characteristics and magnitude of the degradation process effectively acting on antibiotics. A specific case is that of sulfonamides (SAs), one of the antibiotic groups most widely used in veterinary medicine, and which are considered the most mobile antibiotics, causing that they are frequently detected in both surface- and ground-waters, facilitating their entry in the food chain and causing public health hazards. In this work we investigated abiotic and biotic degradation of three sulfonamides (sulfadiazine -SDZ-, sulfachloropyridazine -SCP-, and sulfamethazine -SMT-) in aqueous media. The results indicated that, in filtered milliQ water and under simulated sunlight, the degradation sequence was: SCP > SDZ ≈ SMT. Furthermore, the rate of degradation clearly increased with the raise of pH: at pH 4.0, half-lives were 1.2, 70.5 and 84.4 h for SCP, SDZ and SMT, respectively, while at pH 7.2 they were 2.3, 9.4 and 13.2 h for SCP, SMT and SDZ. The addition of a culture medium hardly caused any change in degradation rates as compared to experiments performed in milliQ water at the same pH value (7.2), suggesting that in this case sulfonamides degradation rate was not affected by the presence of some chemical elements and compounds, such as sodium, chloride and phosphate. However, the addition of bacterial suspensions extracted from a soil and from poultry manure increased the rate of degradation of these antibiotics. This increase in degradation cannot be attributed to biodegradation, since there was no degradation in the dark during the time of the experiment (72 h). This indicates that photo-degradation constitutes the main removal mechanism for SAs in aqueous media, a mechanism that in this case was favored by humic acids supplied with the extracts from soil and manure. The overall results could contribute to the understanding of the environmental fate of the three sulfonamides studied, aiding to program actions that could favor their inactivation, which is especially relevant since its dissemination can involve serious environmental and public health risks.

Biotic and abiotic dissipation of tetracyclines using simulated sunlight and in the dark.

Veterinary antibiotics reaching soils and water bodies are considered emerging pollutants deserving special attention. In this work, dissipation of tetracycline (TC), oxytetracycline (OTC) and chlortetracycline (CTC) is investigated. Dissipation experiments in filtered water, using simulated sunlight, resulted in the following degradation sequence: TC < OTC ≈ CTC, with half-life values of 229, 101 and 104 min, respectively; however, no dissipation took place in the dark. Dissipation of the three tetracyclines in culture medium and with simulated sunlight was much higher, giving the sequence TC ≈ OTC < CTC, with half-lives of 9, 10 and 7 min, respectively; in the dark, TC and OTC did not suffer dissipation, but it was around 28% for CTC at the end of the experiment (480 min). The variable explaining a higher dissipation in culture medium and with light was pH, as this parameter caused changes in the distribution of species of tetracyclines, affecting degradation. Adding bacterial suspensions extracted from soil and poultry manure increased dissipation, giving the sequence: TC ≈ OTC < CTC, which is attributed to the presence of humic acids, which adsorb these antibiotics. These results could facilitate understanding the fate of antibiotics reaching environmental compartments and causing public health hazards.

Retention and transport of mecoprop on acid sandy-loam soils.

Interaction with soil components is one of the key processes governing the fate of agrochemicals in the environment. In this work, we studied the adsorption / desorption and transport of mecoprop (methylchlorophenoxypropionic acid or MCPP) in four acid sandy-loam soils with different organic matter contents. Kinetics of adsorption and adsorption/desorption at equilibrium were studied in batch experiments, whereas transport was studied in laboratory columns. Adsorption and desorption were found to be linear or nearly-linear. The kinetics of mecoprop adsorption were relatively fast in all cases (less than 24h). Adsorption and desorption were adequately described by the linear and Freundlich models, with KF values that ranged from 0.7 to 8.8Ln µmol1-nkg-1 and KD values from 0.3 to 3.6Lkg-1. The results of the transport experiments showed that the retention of mecoprop by soil was very low (less than 6.2%). The retention of mecoprop by the soils in all experiments increased with organic matter content. Overall, it was observed that mecoprop was weakly adsorbed by the soils, what would result in a high risk of leaching of this compound in the environment.

Removal of anionic pollutants by pine bark is influenced by the mechanism of retention.

The use of organic biosorbents for anion removal from water has been less studied than for cationic compounds. In this work, the removal capacity of pine bark for potential anionic pollutants (fluoride, phosphate, arsenate and dichromate) was assessed in column experiments, designed to study the process of transport. The results showed that pine bark has a very low retention capacity for phosphate, arsenate or fluoride, and in turn, very high for dichromate, with retention values close to 100% and less than 2% desorption of the adsorbed dichromate. The large differences observed between anions suggest that differences in the retention mechanism of each anion exist. In the case of phosphate and arsenate, electrostatic interactions with the mostly negatively charged functional groups of the pine bark determine the low retention capacity. Dichromate retention might proceed through reduction of chromium (VI) to chromium (III), what improves the efficiency of the removal.

Study of metal transport through pine bark for reutilization as a biosorbent.

The potential utilization of pine bark as a biosorbent for the treatment of metal-contaminated soils and waters has been evaluated in transport experiments using laboratory columns. Solutions containing the metals Cu, Pb, Zn, Ni or Cd, each one individually and at three different concentrations (2.5, 10 and 25 mM) were tested. Pine bark affected metal transport and the breakthrough curves, producing a reduction of their concentrations in the solution and a clear retardation with respect to an inert tracer. At metal concentrations equal to 2.5 mM, 100% of the assayed elements were removed from the solution in the pine bark column. At the 10 mM metal concentration, the percentage of metals retained fell to 38-67% of the amount added, whereas at the 25 mM metal concentration, only 16-43% was retained. In all cases, the highest retention capacity corresponded to Pb, and the lowest to Zn, whereas Cu, Cd and Ni produced intermediate comparable results. The analysis of the pine bark within the columns after the transport experiment showed that the metals entering the column adsorb progressively until a saturation concentration is reached in the whole column, and only then they can be released at significant concentrations. This saturation concentration was approximately 70 mmol kg(-1) for Cd, Ni and Zn, 100 mmol kg(-1) for Cu, and 125 mmol kg(-1) for Pb. Overall, our experiments have shown the high effectiveness of pine bark to retain the assayed metals in stable forms of low mobility.

Pine bark as bio-adsorbent for Cd, Cu, Ni, Pb and Zn: batch-type and stirred flow chamber experiments.

The objective of this work was to determine the retention of five metals on pine bark using stirred flow and batch-type experiments. Resulting from batch-type kinetic experiments, adsorption was rapid, with no significant differences for the various contact times. Adsorption was between 98 and 99% for Pb(2+), 83-84% for Cu(2+), 78-84% for Cd(2+), 77-83% for Zn(2+), and 70-75% for Ni(2+), and it was faster for low concentrations, with Pb suffering the highest retention, followed by Cu, Cd, Ni and Zn. The fitting to the Freundlich and Langmuir models was satisfactory. Desorption increased in parallel to the added concentrations, with Pb always showing the lowest levels. Stirred flow chamber experiments showed strong hysteresis for Pb and Cu, sorption being mostly irreversible. The differences affecting the studied heavy metals are mainly due to different affinity for the adsorption sites. Pine bark can be used to effectively remove Pb and Cu from polluted environments.

Heavy metal retention in copper mine soil treated with mussel shells: batch and column experiments.

Batch and column experiments are used to study the effects of ground mussel shell amendment on the retention of heavy metals in acidic mine soil. The soil pH increases proportionally with the mussel shell concentration employed. Mussel shell amendment increases Cu, Cd, Ni and Zn retention in mine soil when compared with unamended soil. In fact, Cu retention was 6480µmolkg(-1) (43% of the total added) when the maximum metal concentration (1570µM) was added to the unamended soil, whereas retention reached 15,039µmolkg(-1) (99.9% of the total Cu added) when soil was amended with 24gkg(-1) mussel shell; in the case of Cd, adsorption increases from 3257µmolkg(-1) (15% of the total added) for the unamended soil, to 13,200µmolkg(-1) (87% of the total added) for the shell-amended soil; Ni retention increased from 3767µmolkg(-1) (25% of the total added) corresponding to unamended soil, to 11,854µmolkg(-1) (77% of the total added) for the shell-amended soil; and finally, Zn retention increased from 4684µmolkg(-1) (31% of the total added), for unamended soil, to 14,952µmolkg(-1) (98% of the total added) for shell-amended soil. The results of the constant flow transport experiments show that the addition of the 24gkg(-1) mussel shells can retain Cu, Cd, Ni and Zn within the first few centimetres of the column length, indicating the usefulness of ground mussel shells to drastically decrease the mobility and availability of these pollutants and to facilitate soil remediation.

Copper fractionation and release from soils devoted to different crops.

We studied copper release as a function of pH in eight samples of acid soils under vine and maize crops containing variable concentrations of total copper (Cu(t)) from 55 to 112 mg kg(-1). Although both types of soil had similar Cu(t) values, the origin of the copper was essentially anthropogenic in the vineyard soils and natural (as result of weathering of parent material) in those under maize. The disparate origin of the metal resulted in marked differences in its fractions, particularly as regards organically bound copper, which was much more abundant in the vineyard soils. This had a strong effect on copper release as a function of pH, which was one order of magnitude greater in the vineyard soils than in those under maize.

Quaternary herbicides retention by the amendment of acid soils with a bentonite-based waste from wineries.

The agronomic utility of a solid waste, waste bentonite (WB), from wine companies was assessed. In this sense, the natural characteristics of the waste were measured, followed by the monitoring of its effects on the adsorption/desorption behaviour of three quaternary herbicides in acid soils after the addition of increasing levels of waste. This was done with the intention of studying the effect of the added organic matter on their adsorption. The high content in C (294 g kg(-1)), N (28 g kg(-1)), P (584 mg kg(-1)) and K (108 g kg(-1)) of WB turned it into an appropriate amendment to increase soil fertility, solving at the same time its disposal. WB also reduced the potential Cu phytotoxicity due to a change in Cu distribution towards less soluble fractions. The adsorption of the herbicides paraquat, diquat and difenzoquat by acid soils amended with different ratios of WB was measured. In all cases, Langmuir equation was fitted to the data. Paraquat (PQ) and diquat (DQ) were adsorbed and retained more strongly than difenzoquat (DFQ) in the acid soil studied. However, the lowest retention of DFQ in an acid soil can be increased by amendment with organic matter through a solid waste from wineries, and it is enough for duplicate retention a dosage rate of 10t/ha. Anyway, detritivores ecology can still be affected. Detritivores are the organisms that consume organic material, and in doing so contribute to decomposition and the recycling of nutrients. The term can also be applied to certain bottom-feeders in wet environments, which play a crucial role in benthic ecosystems, forming essential food chains and participating in the nitrogen cycle.

Influence of organic matter removal on competitive and noncompetitive adsorption of copper and zinc in acid soils.

We studied competitive and noncompetitive adsorption of copper and zinc in four acid soils, and compared the behavior of the two metals in untreated samples and samples treated with hydrogen peroxide to remove organic matter in the soil. Copper exhibited stronger competitive adsorption than zinc in the untreated samples. However, removal of organic matter reduced copper adsorption to a greater extent than zinc adsorption, the two metals exhibiting a more similar adsorption pattern than the untreated samples. The presence of copper dramatically reduced zinc competitive adsorption in untreated samples; on the other hand, that of zinc only resulted in slightly reduced competitive adsorption of copper. The hydrogen peroxide treatment decreased competitive adsorption in both metals; however, copper continued to be more efficient than zinc in competing for binding sites on adsorbing surfaces. Desorption of Cu occurred much less readily than desorption of Zn and hysteresis is apparent especially for Cu.

Changes in soil properties and in the growth of Lolium multiflorum in an acid soil amended with a solid waste from wineries.

The agronomic utility of a solid waste, waste perlite (WP), from wine companies was assessed. In this sense, the natural characteristics of the waste were measured, followed by the monitoring of its effects on the chemical properties of acid soils and the growth of Lolium multiflorum. Taking into account that heavy metals associated to the waste (such as Cu, Zn and Mn) could cause problems when used as amendment, the changes in their total levels and in their soil fractionation were also studied, together with their total contents in L. multiflorum. The high content in C (214gkg(-1)), N (25gkg(-1)), P (534mgkg(-1)) and K (106gkg(-1)) of WP turned it into an appropriate amendment to increase soil fertility, solving at the same time its disposal. WP contributed to increase soil pH (in 2 pH units) and cation exchange capacity (CEC increased in 3cmolckg(-1)units), but reduced the potential Cu phytotoxicity due to a change in Cu distribution towards less soluble fractions. The growth of L. multiflorum adequately responds to the treatment with WP at addition rates below 2.5gkg(-1), whereas the imbalance between nutrients can justify the reduction in biomass production at higher WP addition rates. The levels of heavy metals analyzed in L. multiflorum biomass (8-85gkg(-1)) do not seem to cause undesirable effects on its growth.

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

Seasonal distributions of fungicides in soils and sediments of a small river basin partially devoted to vineyards.

The acid soils of Ourense province riverland (Galicia, NW Spain) produce about 50,000 tons of grapes for winemaking. As part of ongoing investigations into fungicide transport in Ourense vineyard soils, the occurrence of several fungicides in such soils was investigated. Soil samples were collected from the inter-row topsoil of a vineyard adjacent to the River Alongos, approximately 15 km SW of the main city of Ourense. The vines were grown in sandy loam with moderate organic carbon (OC) content (1-2%). Fungicide residues were measured in vineyard soils and river sediments by solid-liquid extraction followed by gas chromatography with mass spectrometric detection (GC-MSD). Procymidone and cyprodinil occurred at higher levels in river sediments than in the case of fludioxonil, metalaxyl and penconazole. The highest concentrations of procymidone in sediments were still low (29-57 microg/kg or ppb) suggesting that no accumulation of these compounds occur. All of them were found at higher concentrations in soil; maxima concentrations were about 1000 microg/kg for procymidone and metalaxyl, and about 400 microg/kg for cyprodinil, fludioxonil and penconazole. Folpet was never detected (detection limit lower than 2 microg/kg) in soil and sediments, suggesting that this fungicide was unstable in such samples. The frequency of fungicide detections in soils can be related to their applications in vineyards and the effect of washing off through vineyard canopy by rainfalls. The results found suggest that the vineyard soils of this region are unlikely to be prone to transport of fungicides, and therefore water supplies in this area are unlikely to be at any significant risk of contamination through viticultural use of these compounds.

Atmospheric Pb deposition in Spain during the last 4600 years recorded by two ombrotrophic peat bogs and implications for the use of peat as archive.

Two ombrotrophic peat bogs in Northwestern Spain provided a history of 4600 years of Pb accumulation. Highest Pb concentrations (84-87 microg g(-1)) were found near the bogs' surface, but there were also other significant peaks (6-14 microg g(-1)), indicating pre-industrial atmospheric pollution. The enrichment factors (EFs) in both cores show a remarkably similar record. Atmospheric Pb pollution dates back to at least approximately 2500 years ago, reaching a first maximum during the Roman period. For the last 300 years, Pb EFs significantly increased due to industrial development, but the uppermost samples of the bogs show decreasing Pb EFs, probably due to the phasing out of leaded gasoline. These results are also supported by 206Pb/207Pb isotope ratios, as they continuously decrease from ca. 3000 BP until 2000 BP (from 1.275 at 4070 14C years BP to 1.182), indicating the growing importance of nonradiogenic Pb released from Iberian ores by ancient mining. Peat samples at a 3-5-cm depth are even less radiogenic (206Pb/107Pb = 1.157), indicating the strong influence of leaded gasoline. Despite the common history shared by the two bogs, striking differences were found for Pb enrichment, whether this was calculated by normalising to the Pb/Ti ratio of the upper continental crust or to the Pb/Ti ratios of peats from pre-anthropogenic times. This effect seems to be related to differences in Ti accumulation in both bogs, possibly due to physical fractionation of the airborne dust during wind transport. Enrichment has to be carefully considered when comparing the results obtained for different bogs, since our results suggest that normalising to crustal proportions is meaningless when the bulk of the deposition in an area is strongly influenced by short- and medium-range dust transport.