Soil eutrophication in seabird colonies affects cell wall composition: Implications for the conservation of rare plant species.

Seabird colonies exert a strong influence on coastal ecosystems, increasing soil nitrogen bioavailability and modifying plant communities. Previous studies have evidenced that increased N in soils leads to changes in plant cell wall composition; however, this effect has not been assessed in seabird colonies. The main objective of this study was to determine the influence of seabird colonies on nitrogen, cellulose and lignin content in cell walls. For this purpose, analyses were performed on droppings, soils and three native plant species (Armeria pubigera, Armeria pungens and Corema album) growing in yellow-legged gull colonies. The results showed that N excreted by yellow-legged gull is assimilated by plants, increases N content in plant tissues and reduces cellulose and lignin synthesis, therefore potentially altering plant resistance against phytoparasites.

Geographical variations in arsenic contents in rice plants from Latin America and the Iberian Peninsula in relation to soil conditions.

Arsenic is a ubiquitous, toxic element that is efficiently accumulated by rice plants. This study assessed the spatial variability in the total As (tAs) contents and organic and inorganic forms in different types of rice, plant parts (husk, stem, leaves and phytoliths) and residues. Samples were collected in different countries in Latin America (Ecuador, Brazil and Peru) and the Iberian Peninsula (Spain and Portugal). The tAs content in commercial polished rice from the Latin American countries was similar (0.130-0.166 mg kg-1) and significantly lower than in the rice from the Iberian countries (0.191 ± 0.066 mg kg-1), and together, the tAs concentration in brown rice (236 ± 0.093 mg kg-1) was significantly higher than in polished and parboiled rice. The inorganic As (iAs) content in rice was similar in both geographical regions, and the aforementioned difference was attributed to dimethylarsinic acid (DMA). The relative abundance of organic species increased as the tAs content in rice grain increased. A meta-analysis of our and previously reported data confirmed the negative correlation between iAs/tAs and tAs. At low tAs concentrations, inorganic forms are dominant, while at higher values (tAs > 0.300 mg kg-1) the concentration of organic As increases substantially and DMA becomes the dominant form in rice grain. On the contrary, inorganic arsenic was always the dominant form, mainly as arsenate [As(V)], in leaves and stems. The presence in soils of high concentrations of amorphous Fe and Al oxides and hydroxides, which are capable of strongly adsorbing oxyanions (i.e. arsenate), was associated with low concentrations of As in rice plants. In addition, the presence of high concentrations of As(V) in stems and leaves, low concentration of As in phytoliths, and the As associated with organic matter in stems and husk, together suggest that rice plants take up more As(V) than As(III).

The potential of a Technosol and tropical native trees for reclamation of copper-polluted soils.

Technosols created to reclaim degraded soils is a promising solution that needs further research. The objectives of the study were: i) to create a Technosol with a very high capacity to immobilize copper from mining, ii) to assess the capacity of the Technosol to immobilize copper after planting two tropical native tree species, and iii) to analyse the capacity of the native trees for extracting copper from polluted soils. Myracrodruon urundeuva (aroeira) and Cedrela fissilis (pink cedar) were planted in pots with Technosol spiked with copper at concentrations of 125, 1525 and 3050 mg Cu kg-1. Height and stem diameter were measured over 90 days. Biomass and Cu concentration in leaves, stem and roots were determined. Copper was analysed in soils by sequential extraction, as well as in leached water. The Technosol showed a very high capacity to immobilize copper, since 60-80% of the added copper was strongly retained in the soil, mainly by bentonite and carbonates. The Technosol with trees showed the same capacity to immobilize copper as the control, since concentration in shoots was higher than 300 mg Cu kg-1 and concentration in roots was even higher. These results show that Technosol and both species are useful tools to immobilize copper in polluted soils. Further studies are necessary to determine the total capacity of these trees to immobilize and/or extract copper in the long term and under field conditions.

Trace elements in biomaterials and soils from a Yellow-legged gull (Larus michahellis) colony in the Atlantic Islands of Galicia National Park (NW Spain).

Seabird colonies drastically transform the sites that they inhabit. Although the influence of seabirds on nutrient cycling has been investigated in numerous studies, the effects on trace elements has scarcely been considered. In this study, we determined the total contents of 9 trace elements in biomaterials (excrement, pellets, feathers and eggs) and soils in relation to the presence the Yellow-legged gull Larus michahellis. The concentrations of Zn, Cu and As were particularly high in the pellets and excrement. The total contents of the trace elements were significantly higher in the soils in the sub-colonies in which Yellow-legged gulls predominate than in soil from the control zone (with no gulls). The difference was even higher for the most reactive geochemical fractions. We observed that the oxidizable fraction was the most relevant fraction for almost all trace elements, indicating the importance of organic matter in trace element retention in sandy soils.

Screening of native tropical trees for phytoremediation in copper-polluted soils.

Due to the limited number of studies on phytoremediation using native tree species in tropical soils, the aim was to identify new phytoremediator species from tropical climate with the purpose of promoting an increase in the diversity of tropical native trees used in phytoremediation projects. Seven native tree species from Brazil were selected: Cedrela fissilis, Handroanthus serratifolius, Copaifera langsdorffii, Hymenaea courbaril, Mimosa caesalpiniifolia, Cecropia sp. and Myracrodruon urundeuva. Seedlings of these species were planted in pots with an unpolluted Arenosol, and then spiked with 60, 100 and 500 mg kg-1 Cu. Height and stem diameters were measured over 60 days. Biomass and total Cu concentration were determined in leaves, stem and roots. Copper in bulk soils and rhizospheres was analyzed by a sequential extraction method. All species accumulated high concentration of Cu in roots (>300 mg kg-1), so they could be used as phytostabilizators for this metal. Copper mobilization increased in the rhizospheres, but it was mostly absorbed by roots. Cecropia sp., M. urundeuva and C. langsdorffii are hyperaccumulators of Cu (>300 mg kg-1 in shoots), so they are potential phytoextractor species. This study evidence the potential of seven tree species native from tropical regions for phytostabilizing copper-polluted soils.

High heterogeneity in soil composition and quality in different mangrove forests of Venezuela.

Mangrove forests play an important role in biogeochemical cycles of metals, nutrients, and C in coastal ecosystems. However, these functions could be strongly affected by the mangrove soil degradation. In this study, we performed an intensive sampling characterizing mangrove soils under different types of environment (lagoon/gulf) and vegetation (Rhizophora/Avicennia/dead mangrove) in the Venezuelan coast. To better understand the spatial heterogeneity of the composition and characteristics of the soils, a wide range of the soil attributes were analyzed. In general, the soils were anoxic (Eh < 200 mV), with a neutral pH and low concentration in toxic metals; nevertheless, they varied widely in the soil and its quality-defining parameters (e.g., clay contents, total organic carbon, Fe, Al, toxic trace metals). It is noteworthy that the mangroves presented a low FePyrite content due to a limitation in the Fe oxyhydroxide contents, especially in soils with higher organic C content (TOC > 15%). Finally, the dead mangrove showed significantly lower amounts of TOC and fibers (in comparison to the well-preserved mangrove forest), which indicates that the C pools in mangrove soils are highly sensitive also to natural impact, such as ENSO.

High fragility of the soil organic C pools in mangrove forests.

Mangrove forests play an important role in biogeochemical cycle of C, storing large amounts of organic carbon. However, these functions can be controlled by the high spatial heterogeneity of these intertidal environments. In this study were performed an intensive sampling characterizing mangrove soils under different type of vegetation (Rhizophora/Avicennia/dead mangrove) in the Venezuelan coast. The soils were anoxic, with a pH~7; however other soil parameters varied widely (e.g., clay, organic carbon). Dead mangrove area showed a significant lower amounts of total organic carbon (TOC) (6.8±2.2%), in comparison to the well-preserved mangrove of Avicennia or Rhizophora (TOC=17-20%). Our results indicate that 56% of the TOC was lost within a period of 10years and we estimate that 11,219kgm-2 of CO2 was emitted as a result of the mangrove death. These results represent an average emission rate of 11.2±19.17tCO2ha-1y-1.

Arsenic in rice agrosystems (water, soil and rice plants) in Guayas and Los Ríos provinces, Ecuador.

Geogenic arsenic (As) can accumulate and reach high concentrations in rice grains, thus representing a potential threat to human health. Ecuador is one of the main consumers of rice in South America. However, there is no information available about the concentrations of As in rice agrosystems, although some water bodies are known to contain high levels of the element. We carried out extensive sampling of water, soil, rice plants and commercial rice (obtained from local markets). Water samples were analysed to determine physico-chemical properties and concentrations of dissolved arsenic. Soil samples were analysed to determine total organic C, texture, total Fe and amorphous Fe oxyhydroxides (FeOx), total arsenic (tAs) and the bioavailable fraction (AsMe). The different plant parts were analysed separately to determine total (tAs), inorganic (iAs) and organic arsenic (oAs). Low concentrations of arsenic were found in samples of water (generally <10µgl-1) and soil (4.48±3mgkg-1). The tAs in the rice grains was within the usual range (0.042-0.125mgkg-1 dry weight, d.w.) and was significantly lower than in leaves (0.123-0.286mgkg-1 d.w.) and stems (0.091-0.201mgkg-1 d.w.). The FeOx and tAs and also AsMe in flood water were negatively correlated with tAs in the plants. However, the concentrations of As in stems and leaves were linearly correlated with tAs in the soil and flood water. The relationship between tAs and arsenic in the grain fitted a logarithmic function, as did that between tAs in the grain and the stem. The findings seem to indicate that high concentrations of arsenic in the environment (soil or water) or in the rice stem do not necessarily imply accumulation of the element in the grain. The iAs form was dominant (>80%) in all parts of the rice plants.

Phosphorus in seagull colonies and the effect on the habitats. The case of yellow-legged gulls (Larus michahellis) in the Atlantic Islands National Park (Galicia-NW Spain).

During the period 1980-2000, the yellow-legged gull population underwent exponential growth due to an increase in the availability of anthropogenic food resources. The aim of this study was to highlight the effect of the gull colonies on the P soil cycle and the associated effects on coastal ecosystems. Samples of soil, water and faecal material were collected in a colony of yellow-legged gulls (Cíes Islands) and in a control area. Four sampling plots were installed in the study areas, and samples were collected in summer and winter in 1997 and 2011. Sample analysis included soil characterization and determination of the total P content (TP), bioavailable-P and fractionated-P forms in the soils and faecal material. The (31)P NMR technique was also used to determine organic P forms. Clear differences between the gull colony soils and the control soil were observed. The TP was 3 times higher in the gull colony soil, and the bioavailable P was 30 times higher than in the control soil. The P forms present at highest concentrations in the faecal material (P-apatite, P-residual and P-humic acid) were also present at high concentrations in the colony soil. The absence of any seasonal or annual differences in P concentration indicates that the P has remained stable in the soil over time, regardless of the changes in the gull population density. The degree of P saturation indicated that soils are saturated with P due to the low concentration of Fe/Al-hydroxides, which is consistent with a high P concentration in the run-off from the colonies. The P output from the colony soils to coastal waters may cause eutrophication of a nearby lagoon and the disappearance of a Zostera marina seagrass meadow. Similarly, the enrichment of P concentration in dune system of Muxieiro may induce irreversible changes in the plant communities.

Phosphorus geochemistry in a Brazilian semiarid mangrove soil affected by shrimp farm effluents.

Wastewater discharge from shrimp farming is one of the main causes of eutrophication in mangrove ecosystems. We investigated the phosphorus (P) geochemistry in mangrove soils affected by shrimp farming effluents by carrying out a seasonal study of two mangrove forests (a control site (CS); a site affected by shrimp farm effluents (SF)). We determined the soil pH, redox potential (Eh), total organic carbon (TOC), total phosphorus (TP), and dissolved P. We also carried out sequential extraction of the P-solid phases. In SF, the effluents affected the soil physicochemical conditions, resulting in lower Eh and higher pH, as well as lower TOC and higher TP than in CS. Organic P forms were dominant in both sites and seasons, although to a lesser extent in SF. The lower TOC in SF was related to the increased microbial activity and organic matter decomposition caused by fertilization. The higher amounts of P oxides in SF suggest that the effluents alter the dominance of iron and sulfate reduction in mangrove soils, generating more reactive Fe that is available for bonding to phosphates. Strong TP losses were recorded in both sites during the dry season, in association with increased amounts of exchangeable and dissolved P. The higher bioavailability of P during the dry season may be attributed to increased mineralization of organic matter and dissolution of Ca-P in response to more oxidizing and acidic conditions. The P loss has significant environmental implications regarding eutrophication and marine productivity.

Trace metal pyritization variability in response to mangrove soil aerobic and anaerobic oxidation processes.

The degree of iron pyritization (DOP) and degree of trace metal pyritization (DTMP) were evaluated in mangrove soil profiles from an estuarine area located in Rio de Janeiro (SE Brazil). The soil pH was negatively correlated with redox potential (Eh) and positively correlated with DOP and DTMP of some elements (Mn, Cu and Pb), suggesting that pyrite oxidation generated acidity and can affect the importance of pyrite as a trace metal-binding phase, mainly in response to spatial variability in tidal flooding. Besides these aerobic oxidation effects, results from a sequential extraction analyses of reactive phases evidenced that Mn oxidized phase consumption in reaction with pyrite can be also important to determine the pyritization of trace elements. Cumulative effects of these aerobic and anaerobic oxidation processes were evidenced as factors affecting the capacity of mangrove soils to act as a sink for trace metals through pyritization processes.

Sand as a relevant fraction in geochemical studies in intertidal environments.

Soil and sediment samples from several intertidal environment exposed to different types of contamination were studied to investigate the importance of grain size in relation to the capacity of the substrates to retain trace metals. The unfractionated samples (referred to as bulk samples) were separated into the following grain/size fractions: fine-coarse sand (2-0.100 mm), very fine sand (0.100-0.050 mm), silt (0.050-0.002 mm), and clay (0.002 mm). The sample into its fractions was carried out was in a glove box under high-purity N2 atmosphere in order to minimize any alterations to the samples. The bulk samples were characterized in terms of physicochemical properties such as pH, redox potential, and grain size. The total organic carbon (TOC), total sulfur (S), iron (Fe) pyrite, Fe, and manganese (Mn), and trace metals lead (Pb), mercury (Hg), chromium (Cr), and nickel (Ni) were analyzed in the bulk samples and in each fraction. The sand fractions were also examined by scanning electron microscopy (SEM). Comparisons of the above parameters were made between fractions and between each fraction and the corresponding bulk sample. The fine-coarse sand fraction contained high levels of the primary elements of the geochemical processes that occur in marine sedimentary environments such as TOC, total Fe, Mn, and S. The net concentrations of these four elements were higher in the fine-coarse sand fraction than in the very fine sand fraction and were similar to the net concentrations in the silt and clay fractions. Detailed SEM analysis of the sand coarse fraction revealed the presence of Fe and aluminum oxyhydroxide coatings in the oxic layers, whereas the framboidal pyrites and coatings observed in the anoxic layers were Fe sulfides. The presence of the various coatings explains why the trace metal concentrations in the sand fine-coarse fraction were similar to those in the clay fraction and higher than those in the very fine sand fraction. The present results highlight the importance of the sand fraction, which is generally disregarded in geochemical and environmental studies of sedimentary layers.

Iron and sulfur geochemistry in semi-arid mangrove soils (Ceará, Brazil) in relation to seasonal changes and shrimp farming effluents.

Iron and sulfur are key elements in the biogeochemistry of estuarine soils, in which Fe and sulfate reduction (SR) pathways are important for organic matter decomposition. In the semi-arid coast of NE Brazil, mangroves are characterized by large seasonal variations in weather and the presence of numerous shrimp farms. The objective was to determine the impacts of shrimp farm effluents on iron and sulfur geochemistry in mangrove soils under the semi-arid climate of NE Brazil. A seasonal study was made of two mangrove forest soils (SF, a mangrove forest that directly receives wastewater from shrimp ponds and CS, a control site). Pyrite Fe, oxyhydroxides Fe, acid volatile sulfide, degree of pyritization (DOP), pH, Eh, total organic carbon (TOC) and total S were determined. There was a clear decrease in pyritic Fe and DOP in the SF soils, which may be related to the anaerobic oxidation of pyrite coupled with nitrate reduction, or to the dominance of denitrification over SR. Lower TOC contents in the SF site suggest that below ground decomposition increased in response to eutrophication. The seasonal variations led to important changes in the semi-arid mangrove soils. During the dry period, both soils experienced oxidizing conditions with remarkable loss of reduced and oxidized forms of Fe, which may have important environmental implications as Fe is biolimiting for marine primary production. The data show that both factors (seasonal weather variations and shrimp effluents) play important roles in the geochemical processes that occur in these soils and, thus, may affect their functioning and maintenance.