Characterization of humic-rich hydrocolloids and their metal species by means of competing ligand and metal exchange--an on-site approach

An improved on-site characterization of humic-rich hydrocolloids and their metal species in aquatic environments was the goal of the present approach. Both ligand exchange with extreme chelators (diethylenetetraaminepentaacetic acid (DTPA), ethylendiaminetetraacetic acid (EDTA)) and metal exchange with strongly competitive cations (Cu(II) were used on-site to characterize the conditional stability and availability of colloidal metal species in a humic-rich German bogwater lake (Venner Moor, Münsterland). A mobile time-controlled tangential-flow ultrafiltration technique (cut-off: 1 kDa) was applied to differentiate operationally between colloidal metal species and free metal ions, respectively. DOC (dissolved organic carbon) and metal determinations were carried out off-site using a home-built carbon analyzer and conventional ICP-OES (inductively-coupled plasma-optical emission spectrometry), respectively. From the metal exchange equilibria obtained on-site the kinetic and thermodynamic stability of the original metal species (Fe, Mn, Zn) could be characterized. Conditional exchange constants Kex obtained from aquatic metal species and competitive Cu(II) ions follow the order Mn > Zn > > Fe. Obviously, Mn and Zn bound to humic-rich hydrocolloids are very strongly competed by Cu(II) ions, in contrast to Fe which is scarcely exchangeable. The exchange of aquatic metal species (e.g. Fe) by DTPA/EDTA exhibited relatively slow kinetics but rather high metal availabilities, in contrast to their Cu(II) exchange.     

Choosing policy instruments for controlling ozone depleting substances in a developing context: the case of Chile

Chile ratified the Montreal Protocol in 1990 which sets out an agenda for the reduction and then elimination of ozone depleting substances (ODS); however, by 1998 the country had not yet defined a strategy to encourage greater compliance, so that in the same year the National Environmental Commission decided to examine the policy options available. This paper examines the process followed to develop this strategy. As a first step it was necessary to look at how far the implicit policy of "business as usual" could be stretched without jeopardizing Chile's compliance obligations. A second step included quantifying compliance costs and their impact on different policy instruments and so policy choice. Finally, the attitudes of decision-makers or participants were identified, by interviews with officials of the different public agents involved, in order to weigh their views about policy. A strategy was proposed, based on this information, which the Chilean regulator has used, although not in its entirety. The methodology developed could well be useful for developing-country Protocol signatories building their own appropriate compliance strategy.     

An Ecological Integrity Index for Littoral Wetlands in Agricultural Catchments of Semiarid Mediterranean Regions

The main goal of the present study was to develop an ecological integrity index for littoral wetland management and conservation in semiarid Mediterranean areas that have been highly impacted by agriculture, including the selection of pressure and state indicators at landscape and wetlands scales that reflect the status, condition, and trends of wetlands ecosystems. We used a causality framework based on the relationship between pressure of anthropogenic activities and the ecological state of wetlands and their catchments, integrating environmental, biologic, economic, and social issues. From the application of 51 indicators in 7 littoral wetlands in the southeastern Iberian Peninsula, we selected 12 indicators (5 at catchment scale and 7 at wetland scale) to constitute the ecological integrity index proposed. The potential nitrogen export per area at catchment scale and the potential relative nitrogen export from the area surrounding the wetlands were the best pressure single predictors of state indicators with a causal relationship with environmental meaning. Wetlands in catchments with more agriculture had less ecological integrity than those in less impacted areas. A wide riparian zone in some wetlands acts as a buffer area, diminishing the effects of intensive agriculture. The index of ecological integrity developed here has a number of essential characteristics that make it a useful tool for ecosystem managers and decision-makers. The index can be used to (1) assess and control ecological integrity, (2) diagnose probable causes of ecological impairment, (3) establish criteria for protecting and restoring wetland ecosystems, and (4) integrate catchment management. Published online     

Landform Classification for Land Use Planning in Developed Areas: An Example in Segovia Province (Central Spain)

Landform-based physiographic maps, also called land systems inventories, have been widely and successfully used in undeveloped/rural areas in several locations, such as Australia, the western United States, Canada, and the British ex-colonies. This paper presents a case study of their application in a developed semi-urban/suburban area (Segovia, Spain) for land use planning purposes. The paper focuses in the information transfer process, showing how land use decision-makers, such as governments, planners, town managers, etc., can use the information developed from these maps to assist them. The paper also addresses several issues important to the development and use of this information, such as the goals of modern physiography, the types of landform-based mapping products, the problem of data management in developed areas, and the distinctions among data, interpretations, and decisions.     

Improvements in the two-dimensional nuclear magnetic resonance spectroscopy of humic substances

Understanding pollutant sorption, bioremediation of these pollutants, and their interactions with humic substances requires knowledge of molecular-level processes. New developments with nuclear magnetic resonance (NMR) experiments and labeled compounds have improved the overall understanding of these mechanisms. The advancements made with two-dimensional NMR show great promise, as structural information and hydrogen-carbon bond connectivity can be discerned. This communication presents the application of improved two-dimensional NMR methods, the double quantum filtered (DQF) correlation spectroscopy (COSY) and echo/anti-echo heteronuclear single quantum coherence (HSQC) experiments, for use in structural studies of humic substances. Both experiments were found to produce significant improvements over the conventional COSY and heteronuclear multiple quantum coherence (HMQC) experiments that have been previously employed in similar studies. The more sensitive echo/anti-echo HSQC experiment produced more cross-peaks with higher resolution when compared with the HMQC spectra. The DQF-COSY significantly suppressed the diagonal signals and allowed numerous signals previously hidden in the standard COSY experiment to be observed. These improvements will aid current characterization strategies of humic substances from soils, sediments, and water and their subsequent reactions with pollutants and microorganisms.     

Impact of long-term pesticide applications on some soil biological parameters

The soil oxidative and anaerobic processes, as well as, the microbial biomass were followed during three years in a cotton farm (Tatuí) where the recommended pesticides have been used for several years, and in an experimental field (S?o Paulo) treated first time with the same pesticides. The oxidative process was monitored by the dehydrogenase (DHA)-activity using triphenyltetrazolium chloride (TTC) as substrate. The anaerobic process was followed by the iron-oxide reduction, and the microbial biomass was estimated by the substrate (glucose)-indiced respiration. Increases in DHA-activity and in the microbial biomass occurred only in the farm soil, with concomitant decreases in iron-reduction. In the experimental field soil, the increases in DHA-activity were followed only by decreases in iron-reduction. Soil characteristics were the determining factor for different biological parameters after pesticide inputs. All the pesticides produced at least one clear but transient effect.     

A field study on residues of four insecticides used in strawberry protection

Abstract

In 1986 strawberry plots were treated with dimethoate, malathion, permethrin and cypermethrin at 80% bloom of primary flowers. In 1987 the plots were sprayed with dimethoate, malathion and permethrin at 30% bloom. Residue analysis of these insecticides on the flowers were analyzed using solvent extraction and gas liquid chromatography. Residue analysis at 0 to 18 days on flowers and fruit showed an exponential decrease. Organophosphates tended to degrade more quickly than synthetic pyrethroids. The results are discussed in the context of an integrated pest management program.     

Investigations of mercury concentrations in walleye and other fish in the Athabasca River ecosystem with increasing oil sands developments

Recent studies have reported an increasing trend of mercury concentrations in walleye (Sander vitreus) from the Athabasca River, north eastern Alberta (Canada); these studies were based on three years of comparison and attributed the mercury increase to expanding oil sands developments in the region. In order to conduct a more comprehensive analysis of mercury trends in fish, we compiled an extensive database for walleye, lake whitefish (Coregonus clupeaformis), northern pike (Esox lucius) and lake trout (Salvelinus namaycush) using all available data obtained from provincial, federal, and industry-funded monitoring and other programs. Evidence for increasing trends in mercury concentrations were examined for each species by location and year also considering fish weight and length. In the immediate oil sands area of the Athabasca River, mercury concentrations decreased (p < 0.001) in walleye and lake whitefish over 1984-2011. In western Lake Athabasca and its delta, mercury concentrations decreased (p < 0.0001) in northern pike (1981-2009) although no trend was evident for walleye (1981-2005) and lake trout (1978-2009). Mercury concentrations in lake trout from Namur Lake, a small lake west of the oil sands area, were higher in 2007 than 2000 (p < 0.0001); it is difficult to ascribe this increase to an oil sands impact because similar increases in mercury concentrations have been observed in lake trout from similar sized lakes in the Northwest Territories. While mercury emissions rates have increased with oil sands development and the landscape become more disturbed, mercury concentrations remained low in water and sediments in the Athabasca River and its tributaries and similar to concentrations observed outside the development areas and in earlier decades. Our fish database was assembled from a series of studies that differed in study purpose, design, and analytical methods. Future monitoring programs investigating mercury trends in fish should be more rigorous in their design.     

Fe(3+)- and Cu(2+)-reduction by phenol derivatives associated with Azure B degradation in Fenton-like reactions

Several phenol derivatives were evaluated regarding their capacities for Fe(3+) and Cu(2+) reduction. Selected compounds were assayed in Fenton-like reactions to degrade Azure B. 3,4-Dihydroxyphenylacetic, 2,5-dihydroxyterephtalic, gallic, chromotropic and 3-hydroxyanthranilic acids were the most efficient reducers of both metallic ions. The reaction system composed of 3-hydroxyanthranilic acid/Fe(3+)/H(2)O(2) was able to degrade Azure B at higher levels than the conventional Fenton reaction (87% and 75% of decolorization after 20min reaction, respectively). Gallic and syringic acids, catechol and vanillin induced Azure B degradations at lower levels as compared with conventional Fenton reaction. Azure B was not degraded in the presence of 10% (v/v) methanol or ethanol, which are OH radical scavengers, confirming the participation of this radical in the degradation reactions. Iron-containing reactions consumed substantially more H(2)O(2) than reactions containing copper. In iron-containing reactions, even the systems that caused a limited degradation of the dye consumed high concentrations of H(2)O(2). On the other hand, the reactions containing Fe(3+), H(2)O(2) and 3-hydroxyanthranilic acid or 3,4-dihydroxyphenylacetic acid were the most efficient on degradation of Azure B and also presented the highest H(2)O(2) consumption. These results indicate that H(2)O(2) consumption occurs even when the dye is not extensively degraded, suggesting that part of the generated OH radicals reacts with the own phenol derivative instead of Azure B.