Proton binding by humic and fulvic acids from pig slurry and amended soils

The knowledge of acid-base characteristics of humic acid (HA) and fulvic acid (FA) fractions of organic amendments and amended soils is of considerable importance for assessing their agronomic efficacy and environmental impact. In this work, the acid-base properties of HAs and FAs isolated from pig slurry, soils amended with either 90 or 150 m(3) ha(-1) yr(-1) of pig slurry for 3 yr, and the corresponding nonamended control soil were investigated by using a current potentiometric titration method. The nonideal competitive adsorption (NICA) model that describes proton binding by two classes of binding sites (carboxylic- and phenolic-type groups) was successfully fit to titration data. With respect to the control soil HA and FA, pig-slurry HA and FA were generally characterized by smaller carboxylic-type group contents, slightly smaller phenolic-type group contents, larger affinities for proton binding by the carboxylic-type groups, and much smaller, in the case of the HA fraction, or similar, in the case of the FA fraction, affinities for proton binding by the phenolic-type groups. Amendment with pig slurry determined a number of modifications in soil HAs and FAs, including decrease of acidic functional group contents, and slight increase of the proton affinity of the carboxylic-type groups. Further, a slight decrease of the affinities for proton binding by the phenolic-type groups of HAs was observed. These effects can have a large impact on the biological availability, mobilization, and transport of macro- and micronutrients, toxic metal ions, and xenobiotic organic cations in pig slurry-amended soils.     

LCA of selective waste collection systems in dense urban areas

This paper presents research concerning the environmental analysis of the selective collection management of municipal solid waste. The main goal of this study is to quantify and to compare, by means of Life Cycle Assessment (LCA), the potential environmental impacts of three selective collection systems modelled on densely populated urban areas. These systems are: the mobile pneumatic, the multi-container and the door-to-door. Impact assessment method based on CML 2 baseline 2000 is applied to the different systems. The study separates and analyzes the collection systems in substages: two urban substages and one inter-city substage. At the urban level, the multi-container system has the least environmental impact of all systems. The mobile pneumatic system has greater environmental impacts in terms of global warming, fresh water aquatic ecotoxicity, terrestrial ecotoxicity, acidification and eutrophication. In this system, the pipes and the pneumatic transport have the greatest impacts. The door-to-door system has a greatest environmental impact in terms of abiotic depletion, ozone layer depletion and human toxicity. An overall evaluation of the three substages, with a sensitivity analysis, indicates that the mobile pneumatic system at an inter-city distance of 20 km shows the greatest environmental impacts and the greatest energy demand. Inter-city transport is key; the results show that from an inter-city distance of 11 km onwards, this becomes the substage which most contributes to global warming impact and energy demand, in all the systems.     

Inputs of heavy metals due to agrochemical use in tobacco fields in Brazil’s Southern Region

Only a few studies have assessed the joint incorporation of heavy metals into agricultural systems based on the range of agrochemicals used on a specific agricultural crop. This study was conducted to assess the heavy metals input through application of the main agrochemicals used in Brazilian tobacco fields. A total of 56 samples of different batches of 5 fertilizers, 3 substrates, 8 insecticides, 3 fungicides, 2 herbicides, and 1 growth regulator commonly used in the cultivation of tobacco in Brazil’s Southern Region were collected from 3 warehouses located in the States of Rio Grande do Sul, Santa Catarina, and Paraná. The total As, Cd, Co, Cr, Cu, Hg, Fe, Mn, Ni, Pb, and Zn content of the samples was then determined and compared with the regulations of different countries and information found in the available literature. The fertilizers were identified as the primary source of heavy metals among the agrochemicals used. Application of pesticides directly to the shoots of tobacco plants contributed very little to the supply of heavy metals. The agrochemicals used in Brazilian tobacco fields provide lower inputs of the main heavy metals that are nonessential for plants than those registered in the international literature for the majority of crop fields in different regions of the world.     

Lead isotope ratios in lichen samples evaluated by ICP-ToF-MS to assess possible atmospheric pollution sources in Havana,Cuba

Epiphytic lichens, collected from 119 sampling sites grown over “Roistonea Royal Palm” trees, were used to assess the spatial distribution pattern of lead (Pb) and identify possible pollution sources in Havana (Cuba). Lead concentrations in lichens and topsoils were determined by flame atomic absorption spectrophotometry and inductively coupled plasma (ICP) atomic emission spectrometry, respectively, while Pb in crude oils and gasoline samples were measured by ICP-time of flight mass spectrometry (ICP-ToF-MS). Lead isotopic ratios measurements for lichens, soils, and crude oils were obtained by ICP-ToF-MS. We found that enrichment factors (EF) reflected a moderate contamination for 71% of the samples (EF > 10). The ²⁰⁶Pb/²⁰⁷Pb ratio values for lichens ranged from 1.17 to 1.20 and were a mixture of natural radiogenic and industrial activities (e.g., crude oils and fire plants). The low concentration of Pb found in gasoline (<7.0 μg L^?1) confirms the official statement that leaded gasoline is no longer used in Cuba.     

Statistical Assumptions Matter in Data Analysis for Texas Ozone Nonattainment Sites

Strategies for control of ozone aim at regulation of its chemical precursors, non-methane organic compounds (NMOC) and nitrogen oxides (NOx). It is therefore important to analyze how these precursors vary temporally and geographically. This study finds significant and important differences among four Texas ozone nonattainment sites, Dallas, Ft. Worth, El Paso, and Houston, for 1984, 1985, and 1986 for NMOC, NOx, and their ratio NNR. These differences were detected through nonparametric analysis of variance and Student-New-man-Keuls’s test for multiple comparisons on rank-transformed data. A noteworthy feature of the data analysis is its attention to the assumptions underlying the statistical methods. Classical models based on normal or lognormal theory had to be abandoned for lack of realism. It is demonstrated how alternative models may be applied to yield appropriate, rather than inappropriate, conclusions.     

Effects of long-term soil amendment with sewage sludges on soil humic acid thermal and molecular properties

Sewage sludges are frequently used as soil amendments due to their high contents of organic matter and nutrients, particularly N and P. However, their effects upon the chemistry of soil humic acids, one of the main components of the soil organic matter, need to be more deeply studied in order to understand the relation between organic matter structure and beneficial soil properties. Two sewage sludges subjected to different types of pre-treatment (composted and thermally dried) with very different chemical compositions were applied for three consecutive years to an agricultural soil under long-term field study. Thermal analysis (TG–DTG–DTA) and solid-state ¹³C NMR spectroscopy were used to compare molecular and structural properties of humic acids isolated from sewage sludges, and to determine changes in amended soils. Thermally dried sewage sludge humic acids showed an important presence of alkyl and O/N-alkyl compounds (70%) while composted sludge humic acids comprised 50% aromatic and carbonyl carbon. In spite of important differences in the initial chemical and thermal properties of the two types of sewage sludges, the chemical and thermal properties of the soil humic acids were quite similar to one another after 3 years of amendment. Long-term application of both sewage sludges resulted in 80–90% enrichment in alkyl carbon and organic nitrogen contents of the soil humic acid fraction.     

Evaluation of several priority pollutants in zebra mussels (Dreissena polymorpha) in the largest Italian subalpine lakes

Zebra mussel (Dreissena polymorpha) has been used for the biomonitoring of several POPs (PCBs, DDTs, HCB and HCHs) in the largest Italian subalpine great lakes (Lake Maggiore, Garda, Como, Iseo and Lugano). Samplings were carried out in April 2003 at 15 locations selected according to industrial and anthropic levels of lakes. Results have pointed out high DDT levels in D. polymorpha specimens from Lake Maggiore (700-1400 ng/g lipids, 5-9 times higher than those measured in mussels of other Italian lakes), due to a contamination from a chemical plant located on one of the main lake inlet that occurred in 1996. On the contrary, PCB levels (400-2509 ng/g lipids) highlighted an overall pollution, with some sporadic peaks of contamination. Data showed a moderate increase trend compared to those found in a previous monitoring campaign carried out in 1996. Future monitoring is needed in order to confirm this tendency.     

Effects of municipal solid waste compost and sewage sludge on chemical and spectroscopic properties of humic acids from a sandy Haplic Podzol and a clay loam Calcic Vertisol in Portugal

The effects of amendment with municipal solid waste compost (MSWC) and anaerobically digested sewage sludge (SS) on the compositional and structural features of soil humic acids (HAs) were investigated. For this purpose, HAs were isolated from MSWC, SS, and two different Portuguese soils, a sandy Haplic Podzol and a clay loam Calcic Vertisol, which were either unamended or amended with MSWC or SS at a rate of 60tha(-1). The isolated HAs were analyzed for elemental and acidic functional group composition, and by ultraviolet/visible, Fourier transform infrared (FT IR), and fluorescence spectroscopies. The application of MSWC and especially SS to soils determined an increase of C, N, H, and S contents and E(4)/E(6) ratios (i.e., ratios of absorbances at 465 and 665nm), and a decrease of O, COOH, and phenolic OH contents and C/N, C/H, and O/C ratios of soil HAs. The FT IR and fluorescence results showed that the organic amendments, especially SS, caused an increase of the aliphatic character and a decrease of the degrees of aromatic polycondensation, polymerization, and humification of amended soil HAs. Both MSWC and SS affected more markedly the clayey soil HAs than the sandy soil HAs, possibly due to less extended mineralization processes and the protective action of clay minerals on amended soil HAs.     

Assessment of the pollution impact on biomarkers of effect of a freshwater fish

Changes in biomarkers of fish captured from stressed environments may represent a reliable tool in revealing sublethal effects of the pollutants found in aquatic ecosystems. The response patterns of selected biochemical and morphological variables biomarkers of effect were assessed in adult females of an indigenous teleost Cnesterodon decemmaculatus, caught at a polluted site (San Francisco) of the Reconquista river (Buenos Aires, Argentina). Combined field-caging experiments with controlled laboratory exposure to clean media were performed. The biochemical parameters measured were specific activities of gill (Na+ + K+)-ATPase, liver AlaAT and AspAT, and brain AChE; LSI and CF were also calculated. The changes in gill (Na+ + K+)-ATPase and liver AlaAT activities of fish captured in the field in most cases were reversible after transfer to clean media. The results were interpreted in association with the physicochemical profile of the water samples taken simultaneously with the capture of the fish. Results suggested the suitability of the test species used as tools in environmental monitoring programs of risk assessment.