Kinetic and equilibrium analysis of penguin guano trace elements release to Antarctic seawater and snow meltwater.

The present work extends the scope of prior studies through analysis, modelling and simulation of the As, Cd, Co, Cu, Fe Mn, Mo, Ni and Zn release from Gentoo (Pygoscelis papua) and Chinstrap (Pygoscelis antarcticus) penguin guano to the Southern Ocean seawater and to Antarctic snow meltwater. Laboratory experimental results have been modelled considering kinetic processes between water and guano using two element pools in the guano compartment; its application allows us to interpret behaviours and predict release concentrations of dissolved trace elements from guano which are potentially useful for incorporation as elements source into biogeochemical models applied in the Southern Ocean. Variations in quantities and release patterns depending on the type of guano and aqueous medium in contact have been identified. The release percentages from the guano to the aqueous medium, once the steady state has been reached, vary depending on the water medium and guano type in the ranges of 100-2.9 % for Mo; 91.5-68.6 % for Ni; 81.8-22.8 % As; 52.0-43.9 % Cu; 26.9-7.4 % Mn; 24.9-5.4 for Co; 4.4-3.2 % for Zn and 0.94-0.51 % for Fe. Considering a penguin population of 774,000 Gentoo and 8,000,000 Chinstrap, the estimated annual mass released to the both seawater and freshwater would be ≈18,500 kg for Cu, ≈1710 kg for Zn, ≈1944 kg for Fe, ≈1640 kg for Mn, ≈499 kg for As, ≈289 kg for Ni, ≈155 kg for Mo, ≈36.7 kg for Cd and ≈8.1 kg for Co. These contributions can be locally significant both in promoting phytoplankton growth and in their role as inhibitors of primary productivity.

Modelling the bioconcentration of Zn from commercial sunscreens in the marine bivalve Ruditapes philippinarum.

Sunscreens contain ZnO particles used as a UV filter cause adverse effects in the marine environment through the release of this metal into seawater and its bioaccumulation in organisms. A mathematical model using sunscreen colloidal residues, seawater and R. philippinarum clams as differentiated compartments, is proposed in order to interpret both the kinetic pattern and the bioaccumulation of Zn in clams. Two kinetic laboratory experiments were conducted, both with and without clams exposed to sunscreen concentrations from 0 to 200 mg L-1. Both the lowest value of uptake rate coefficient obtained when 5 mg L-1 of sunscreen is added (0.00688 L g-1 d-1) and the highest obtained at sunscreen addition of 100 mg L-1 (0.0670 L g-1 d-1), predict a lower bioavailability of Zn in a complex medium such as the seawater-sunscreen mixtures, in comparison to those studied in the literature. The efflux rate coefficient from clams to seawater increased from 0 to 0.162 d-1 with the sunscreen concentrations. The estimated value of the inlet rate coefficient at all studied concentrations indicates that there is a negligible colloidal Zn uptake rate by clams, probably due to the great stability of the organic colloidal residue. An equilibrium shift to higher values of Zn in water is predicted due to the bioconcentration of Zn in clams. The kinetic model proposed with no constant Zn (aq) concentrations may contribute to a more realistic prediction of the bioaccumulation of Zn from sunscreens in clams.

Spatial distribution and level of contamination of potentially toxic elements in sediments and soils of a biological reserve wetland, northern Amazon region of Ecuador.

This study quantifies the degree of pollution and assess the ecological risk of As, Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, V and Zn in sediments and soils of the Limoncocha Biological Reserve (Ecuador), identified as a Ramsar site with high ecological and socioeconomic value. The hydrologic system of the Reserve is mainly formed by two rivers that drain into the Limoncocha lagoon, which occupies only five percent of the protected area but support a high anthropic influence. Local statistical baseline of studied potentially toxic elements is established using cumulative frequency method, and Al is selected as reference element due to the good correlation with the studied elements. The grade of pollution and the potential ecological risk are evaluated applying three individual (Contamination Factor, Geo-accumulation Index and Enrichment Factor) and six integrated (Degree and modified degree of contamination, Pollution Load Index, Nemerow and modified Nemerow pollution indexes and potential ecological risk index) indices. Results analysis are based on the combined application of traditional statistics, multivariate data analysis and self organizing maps. Outcomes suggest to classify sediments and soils as "moderate contamination and enrichment" due mainly to the concentrations of Cu (66.4-110 mg/kg) and Cd (0.0262-0.808 mg/kg), derived from domestic wastewaters and agricultural activities, and in a lesser extent due to Mo (0.822-4.37 mg/kg), Ni (10.3-25.8 mg/kg), Co (7.27-24.8 mg/kg) and V (60.3-178 mg/kg), derived from oil field drilling activities. The distributions of As (0.328-8.83 mg/kg), Ba (143-1100 mg/kg), Pb (7.20-26.5 mg/kg), Zn (60.1-276 mg/kg) and Cr (10.1-48.6 mg/kg) are heterogeneous in the studied sampling sites. Sediments located next to the pier and at the central area of the Limoncocha lagoon, show moderate potential risk and according to sediment quality guidelines, the calculated mean Effect Range Median quotient (mERMq) classify the sites as medium-low priority risk level. A three-level classification of a mean quotient based on soil quality and soil potential uses is proposed. Soil sites with high anthropogenic activities show low to moderate potential ecological risk being classified as poor soil quality sites but with all potential soil uses allowed according to the legal limits for land uses in Ecuador.

Sunscreens as a New Source of Metals and Nutrients to Coastal Waters.

Studies detailing the environmental impact of sunscreen products on coastal ecosystems are considered a high priority. In the present study, we have determined the release rate of dissolved trace metals (Al, Cd, Cu, Co, Mn, Mo, Ni, Pb, and Ti) and inorganic nutrients (SiO2, P-PO43-, and N-NO3-) from a commercial sunscreen in seawater, and the role of UV radiation in the mobilization of these compounds. Our results indicate that release rates are higher under UV light conditions for all compounds and trace metals except Pb. We have developed a kinetic model to establish the release pattern and the contribution to marine coastal waters of dissolved trace metals and inorganic nutrients from sunscreen products. We conservatively estimate that sunscreen from bathers is responsible for an increase of dissolved metals and nutrients ranging from 7.54 × 10-4 % for Ni up to 19.8% for Ti. Our results demonstrate that sunscreen products are a significant source of metals and inorganic nutrients to coastal waters. The normally low environmental concentrations of some elements (e.g., P) and the toxicity of others (e.g., Pb) could be having a serious adverse effect on marine ecology in the Mediterranean Sea. This risk must not be ignored.