Green Approach to Clean Marble Surfaces

In the field of cultural heritage restoration, the removal of iron corrosion stains is a difficult problem to deal with, especially in porous stone materials. Many studies in recent years have been aimed at finding simple and reliable methods using non-toxic chelating compounds. The search for natural compounds is therefore of great relevance, especially in the restoration of cultural heritage, where the use of toxic chemical compounds often involves risks for the environment and human health. Following this trend, the purpose of this preliminary work was to verify the use of two natural proteins, Lactotransferrin (Ltf) and Ovotransferrin (Ovt), for the removal of iron-based stains on marble surfaces. The two proteins, whose high affinity for iron "in vivo" has been widely documented, were extracted from their natural matrices. The protein extracts were then immobilized using a common cellulose pulp. The poultices obtained were spread on the surfaces of artificially stained marble specimens and, after a set time, were easily removed. The effectiveness of the removal, visually evident, was detected by spectrocolorimetry and image analysis. The surface analyses, before and after the treatment, carried out by X-ray photoelectron spectroscopy (XPS), confirmed that both proteins have a selective and effective complexing capacity for the ferric ions of rust stains.

Soil organic carbon mobility in equatorial podzols: soil column experiments

Transfer of organic carbon from topsoil horizons to deeper horizons and to the water table is still little documented, in particular in equatorial environments, despite the high primary productivity of the evergreen forest. Due to its complexing capacity, organic carbon also plays a key role in the transfer of metals in the soil profile and, therefore, in pedogenesis and for metal mobility. Here we focus on equatorial podzols, which are known to play an important role in carbon cycling. We carried out soil column experiments using soil material and percolating solution sampled in an Amazonian podzol area in order to better constrain the conditions of the transfer of organic carbon at depth. The dissolved organic matter (DOM) produced in the topsoil was not able to percolate through the clayey, kaolinitic material from the deep horizons and was retained in it. When it previously percolated through the Bh material, there was production of fulvic-like, protein-like compounds and small carboxylic acids able to percolate through the clayey material and increase the mobility of Al, Fe and Si. Podzolic processes in the Bh can, therefore, produce a DOM likely to be transferred to the deep water table, playing a role in the carbon balances at the profile scale and, owing to its complexing capacity, playing a role in deep horizon pedogenesis and weathering. The order of magnitude of carbon concentration in the solution percolating at depth was around 1.5–2.5 mg L−1. Our findings reveal a fundamental mechanism that favors the formation of very thick kaolinitic saprolites.

Soil organic carbon mobility in equatorial podzols: soil column experiments

Transfer of organic carbon from topsoil horizons to deeper horizons and to water table is still little documented, in particular in equatorial environments despite the high primary productivity of the evergreen forest. Due to its complexing capacity, organic carbon also plays a key role in the transfer of metals in the soil profile and therefore in pedogenesis and for metal mobility. We were interested in equatorial podzols, which are known to play a significant role in carbon cycling. We carried out soil column experiments using soil material and percolating solution sampled in an Amazonian podzol area. The dissolved organic matter (DOM) produced in the topsoil was not able to percolate through the clayey, kaolinitic material from the deep horizons and was retained in it. When it previously percolated through the Bh material, there was production of fulvic-like, protein-like compounds and small carboxylic acids able to percolate through the clayey material and increasing the mobility of Al, Fe and Si. Podzolic processes in the Bh can therefore produce a DOM likely to be transferred to the deep water table, playing a role in the carbon balances at the profile scale, and owing to its complexing capacity, playing a role in deep horizon pedogenesis and weathering. The order of magnitude of carbon concentration in the solution percolating in depth was around 1.5–2.5 mg L−1.

How Much Carbon Do the Soils of Papua New Guinea Forests Contain?

Preliminary assessment of carbon in forest soils of Papua New Guinea (PNG) was done for 53 sites. Simple soil-landscape model was constructed to explain how soil carbon relates to landscape position and landform processes. Despite limitations of the soil survey, sufficient data have been obtained to indicate that the amount of carbon in forest soils surveyed so far is related primarily to their carbon-complexing capacity (CCC) which, in turn, depends on their geological parent material and parent rock. Soils were grouped into six categories based on their carbon content. The six categories ranged from very low 0–50 t/ha to extremely high 601–1,000 t/ha. Amalgamating the areas of mapped geological units on the basis of their likely CCC and their median carbon content has enabled the total carbon content of all forest soils in PNG to be estimated as 7,727 × 106 t. This figure is approximate and will be modified as more results are obtained and more sophisticated GIS-based landscape analysis is undertaken. The total carbon in forest biomass, as measured in this National Inventory and estimated for roots, is 4,006 × 106 t. Thus, the total carbon in PNG’s forests at present is estimated to be 11,733 × 106 t, with 66% stored in the soil and 34% in the biomass. The high proportion of ecosystem carbon held in the soil emphasises the importance of implementing soil conservation measures to maintain the total carbon resource in PNG’s forests.

Increasing soil fertility as an important factor in ensuring food security of the state

The influence of chicken manure compost with sawdust in doses from 100 to 1000 t/ha on soil properties was studied on the sod-podzolic soils where the poultry farms of the Moscow region are located. An increase in pH, the humus content, the content of water-soluble forms of NPK in soils and an increase in the complexing capacity of soils were found. The authors define the correlation of the content of mobile forms of heavy metals in the sod-podzolic soils fertilized with poultry droppings with soil pH, the content of humus and mobile phosphates in them. The permissible doses of manure introduced into the soil as fertilizer are determined by the combination of properties, processes and soil regimes, relief, groundwater level, and hydrothermal conditions of the territory. The introduction of droppings into soils contaminated with heavy metals increased their mobility due to complex formation. A positive effect of the use of humates from chicken droppings on the bioproductivity of plants is defined. The article considers the necessity of controlling the quality of the water and air environment when regulating the composition and doses of application of chicken manure compost.

Physico-Chemical Characterization of an Urban Rainwater (Zagreb, Croatia)

The characterization of organic matter (OM) and trace elements (TEs) was conducted in bulk precipitation samples collected in an urban area of Croatia (Zagreb center), from January 2009 to October 2011 (N = 31). Characterization of OM was performed by measurement of dissolved (DOC) and particulate forms of organic carbon (POC), as well as surface-active substances, copper complexing capacity and reduced sulfur species which were determined electrochemically. Concentrations of TEs (Al, Fe, Zn, Cr, Ba, Mn, Cu, Sr, Ti, Pb, V, Ni, Rb, Sb, As, Sn, Se, Co, Cd, Mo) were analyzed by HR ICP-MS. The most important outcome of this study is confirmed relatively low concentrations of DOC (0.69–4.86 mgC L−1) and TEs. Daily fluxes of Zn, Pb, Ni, As, and Cd were two to three times lower than that of those reported for an urban industrial site in Europe. Additionally, this study shows that the value and reactivity of rainwater DOC has not considerably changed if compared with the results from the 1998–1999 study (0.78–4.39 mgC L−1). High traffic density and thermal power plants are assumed to be the main local sources of pollutants in Zagreb. Using Al as a reference element, it was found that Cd, Sb, and Cu were associated with anthropogenic sources. The solubility of Sr, Zn, Cd, Ni, Cr, As, and Rb was higher than 70%. Another critical characteristic of precipitation composition is episodic variation in POC concentration because of Saharan dust transport. Obtained data can be valuable for environmental quality assessment, as well as for insight into atmospheric deposition processes.

Experimental and DFT study of the effect of mercaptosuccinic acid on cyanide-free immersion gold deposition

A cyanide-free gold plating bath was prepared and the complexing capacity of mercaptosuccinic acid with Au(i) was studied through density functional theory.

Links between size fractionation, chemical speciation of dissolved copper and chemical speciation of dissolved organic matter in the Loire estuary

Environmental contextThe toxicity of copper to aquatic life is highly dependent on its chemical form. In the vineyards of the Loire valley, mixtures of copper compounds are increasingly being used as fungicides. Our study investigating the origin and behaviour of dissolved copper on the land-sea continuum of the Loire advances our understanding of the chemical forms and fate of copper in estuarine systems. AbstractWe present data on the organic speciation of dissolved copper (dCu) in the Loire estuary for the soluble (<0.02µm) and dissolved (<0.45µm) fractions. These results were interpreted according to the distribution of natural organic matter along the estuary. We observed a high concentration of dCu (80nmolkg−1) upstream of the tidal front (S=0.1, where S is the salinity), possibly induced by drainage from vineyards located on the watershed of the estuary, and a concentration typical of coastal seawater at the end of the salinity gradient (3–4nmolkg−1). dCu showed a non-conservative distribution along the estuary with a notably strong decrease in concentration at the very first stage of mixing (S ~ 0.5) that increased again at low salinity (S=4.7). The latter increase in the concentration of dCu was related to the supply of colloidal copper induced by particle desorption in the maximum turbidity zone. The organic speciation of dCu revealed that the complexing capacity of copper ligands (LCu, up to 147 nanomoles of Cu per kilogram of water) exceeded dCu in both the soluble and dissolved fractions, which kept the activity of cupric ions below toxic levels for most unicellular phytoplankton. Humic substances comprised up to 95% of LCu in the continental shelf sample, but their complexing capacity did not account for all of the LCu in the inner estuary. We conducted pseudopolarographic experiments and found two other additional ligand classes: thiol-like and amino-acids/proteins. While humic substances are the dominant component of dissolved organic matter (DOM), the study of DOM suggested the release of colloidal DOM from a wastewater treatment plant. This structure could be a major source of proteinaceous LCu in the system that changes the dCu speciation in the middle of the estuary.

High Performance Size Exclusion Chromatography-Inductively Coupled Plasma-Mass Spectrometry to Study the Copper and Cadmium Complexation with Humic Acids

Dissolved organic matter (DOM) plays an important role in the environment by influencing the transport and distribution of organic and inorganic components through different processes: the retention, mobilization, and bio-availability of potentially toxic elements (PTEs). The aim of the present study is to examine the dimensional characterization of humic acids (HA) extracted from soil matrix, as well as to analyze the metal distribution among different ligand classes. The molecular size distribution of the HA extract from soil showed three dimensional classes: 52 KDa, 4.5 KDa, and 900 Da. HPSEC-ICP-MS measurements demonstrated that the dimensional classes, relative to first two fractions, bind the largest part of metals. The complexing capacity of HA was evaluated to assess the pollutants mobility in the environmental system. In particular, cadmium (Cd) and copper (Cu) complexation was investigated due to the great concern regarding their bio-availability and toxicity in natural waters. The complexing capacity of HA solution (20 mg/L) was measured by titration using a high-performance size exclusion chromatography (HP-SEC) coupled to an inductively coupled mass spectrometry (ICP-MS). Results obtained by this technique are compared with those obtained by anodic stripping voltammetry (ASV) to investigate the effects of kinetic lability of complexes on measurements carried by HPSEC-ICP-MS. In this study, results of ligand concentrations and stability constants obtained via the two techniques are assessed considering the detection window associated to the applied analytical methodology. Results obtained using the two analytical techniques showed that Cd is complexed by two classes of ligands. However, the ligand concentration values obtained using the two techniques are different, because the detection window associated to the two methodologies; the complexing capacity, which was obtained as sum of the two classes of ligands, were 33 nmol/L and 9 nmol/L for ASV and HPSEC-ICP-MS, respectively. The copper complexing capacities determined by the two methodologies are comparable: 166 and 139 nmol/L for ASV and HPSEC-ICP-MS, respectively. However, the results of Cu titration differ for the two techniques, highlighting only one class of ligands when ASV was used, and two classes when HPSEC-ICP-MS was employed. Differences on results obtained by the two techniques are explained considering the kinetic lability of complexes; the results show that, differently from previous studies, also Cu complexes can be kinetically labile, if one technique with high reaction time is used, as well some cadmium complexes are sufficient stable to be determined by HPSEC-ICP-MS.