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.     

Mapping residual pyrite after a mine spill using non co-located spatiotemporal observations

Monitoring of soil chemical properties for pollution assessment generally requires destructive soil sampling and results in spatiotemporal datasets where data from different sampling dates are non co-located. The objective of this study was to assess the spatial distribution of residual pyrite sludge at a reclaimed site, using temporally non co-located data on pH; soil oxidizable fraction (SOF); and EDTA-extractable Fe, Zn, and Cu from six different sampling dates over a period of 2 yr. During this period spatially averaged pH and Zn concentrations ranged, respectively, from 4.4 to 6.6 and from 60 to 140 mg kg(-1), with minimum pH values of below 2.7. The data were merged into a single dataset for each chemical property after applying a normal score (ns) transform. Normal score pH was significantly negatively correlated with the ns metal concentrations. A principal component analysis (PCA) showed that normal score pH, Zn, and Fe were associated with the residual contamination, while ns Cu, SOF, and elevation were related with historic contamination. The spatial dependence between the properties was found to be scale-dependent. The best ns estimates were produced by ordinary kriging with an anisotopic variogram model, for the properties related with Principal Component (PC) I, while those associated with PC II were best estimated using simple kriging with varying local means. A classified ns pH map showed that 33% of the study area reached at least once values of below 4 during the 2-yr period. This part of the area should be excluded to ensure successful revegetation.     

Development and application of a regional-scale atmospheric mercury model based on WRF/Chem: a Mediterranean area investigation

The emission, transport, deposition and eventual fate of mercury (Hg) in the Mediterranean area has been studied using a modified version of the Weather Research and Forecasting model coupled with Chemistry (WRF/Chem). This model version has been developed specifically with the aim to simulate the atmospheric processes determining atmospheric Hg emissions, concentrations and deposition online at high spatial resolution. For this purpose, the gas phase chemistry of Hg and a parametrised representation of atmospheric Hg aqueous chemistry have been added to the regional acid deposition model version 2 chemical mechanism in WRF/Chem. Anthropogenic mercury emissions from the Arctic Monitoring and Assessment Programme included in the emissions preprocessor, mercury evasion from the sea surface and Hg released from biomass burning have also been included. Dry and wet deposition processes for Hg have been implemented. The model has been tested for the whole of 2009 using measurements of total gaseous mercury from the European Monitoring and Evaluation Programme monitoring network. Speciated measurement data of atmospheric elemental Hg, gaseous oxidised Hg and Hg associated with particulate matter, from a Mediterranean oceanographic campaign (June 2009), has permitted the model’s ability to simulate the atmospheric redox chemistry of Hg to be assessed. The model results highlight the importance of both the boundary conditions employed and the accuracy of the mercury speciation in the emission database. The model has permitted the reevaluation of the deposition to, and the emission from, the Mediterranean Sea. In light of the well-known high concentrations of methylmercury in a number of Mediterranean fish species, this information is important in establishing the mass balance of Hg for the Mediterranean Sea. The model results support the idea that the Mediterranean Sea is a net source of Hg to the atmosphere and suggest that the net flux is ≈30 Mg year^?1 of elemental Hg.     

Mercury in the Mediterranean,part I: spatial and temporal trends

The present paper provides an overview of mercury studies performed in the Mediterranean Sea region in the framework of several research projects funded by the European Commission and on-going national programmes carried out during the last 15 years. These studies investigated the temporal and spatial distribution of mercury species in air, in the water column and sediments, and the transport mechanisms connecting them. It was found that atmospheric concentrations of Hg compounds, particularly oxidised Hg species observed at five coastal sites in the Mediterranean Sea Basin, are significantly higher compared with those recorded at five coastal sites distributed across N Europe, most probably due to natural emissions. Hg levels in water are comparable to other oceans. Anthropogenic and natural point sources show locally limited enrichments, while natural diffusive sources influence Hg speciation over larger areas. Results and statistic comparison of mercury species concentrations within Mediterranean compartments will be presented and discussed.     

Industrial sources influence air concentrations of hydrogen sulfide and sulfur dioxide in rural areas of western Canada

A survey of monthly average concentrations of sulfur dioxide (SO2) and hydrogen sulfide (H2S) at rural locations in western Canada (provinces of Alberta, British Columbia, and Saskatchewan) was conducted in 2001-2002, as part of an epidemiological study of the effects of oil and gas industry emissions on the health of cattle. Repeated measurements were obtained at some months and locations. We aimed to develop statistical models of the effect of oil and gas infrastructure on air concentrations. The regulatory authorities supplied the information on location of the different oil and gas facilities during the study period and, for Alberta, provided data on H2S content of wells and flaring volumes. Linear mixed effects models were used to relate observed concentrations to proximity and type of oil and gas infrastructure. Low concentrations were recorded; the monthly geometric mean was 0.1-0.2 ppb for H2S, and 0.3-1.3 ppb for SO2. Substantial variability between repeated measurements was observed. The precision of the measurement method was 0.005 ppb for both contaminants. There were seasonal trends in the concentrations, but the spatial variability was greater. This was explained, in part, by proximity to oil/gas/bitumen wells and (for SO2) gas plants. Wells within 2 km of monitoring stations had the greatest impact on measured concentrations. For H2S, 8% of between-location variability was explained by proximity to industrial sources of emissions; for SO2 this proportion was 18%. In Alberta, proximity to sour gas wells and flares was associated with elevated H2S concentrations; however, the estimate of the effect of sour gas wells in the immediate vicinity of monitoring stations was unstable. Our study was unable to control for all possible sources of the contaminants. However, the results suggest that oil and gas extraction activities contribute to air pollution in rural areas of western Canada.     

Serum levels of PCDDs, PCDFs and PCBs in non-occupationally exposed population groups living near two incineration plants in Tuscany, Italy

A pilot study was carried out in Tuscany, Italy, to provide preliminary information on the concentrations of polychlorinated dibenzodioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorobiphenyls (DL-PCBs), and selected non-dioxin-like PCBs (NDL-PCBs) in groups of subjects living in the vicinity of two incineration plants. Seventy-four volunteers were enrolled from areas identified as under a potential impact from incinerator emissions and from not exposed areas. No significant differences were observed between subjects living in the two types of areas. Total concentrations of PCDDs, PCDFs, and DL-PCBs resulted to be in the range 23-30 pg WHO-TEQ g(-1), lipid base, for subjects in the 27-54 year age groups, while concentrations increased to 40-44 pgTEQ g(-1) for the two 55-67 year age groups. The levels of PCDDs and PCDFs were in good agreement with those observed for unexposed population groups in Italy, while the contribution to total TEQ from DL-PCBs was appreciably higher than those currently observed in the general population in Italy and other countries. As to NDL-PCBs, serum levels of the six "indicator" congeners were in the range 240-300 ng g(-1), lipid base, for subjects in the 27-54 year age groups. A raise in NDL-PCB body burden (430-470 ng g(-1), lipid base) was observed for the two 55+ year age groups, in agreement with the expected age-dependent increase. The findings from this study do not show an incremental exposure to PCDDs and PCDFs in the samples from subjects living around the two incineration plants, whereas PCB congener profiles in all samples suggest a possible impact on the area of interest of industrial activities from near industrial settlements.     

Organochlorine contamination in the Great Crested Grebe (Podiceps cristatus): effects on eggshell thickness and egg steroid levels

Eggs of the Great Crested Grebe (Podiceps cristatus) were collected from a breeding area on Lake Maggiore (Northern Italy) from 2001 to 2005 in the vicinity of a p,p'-DDT manufacturer, whose production was stopped in 1996. DDT homologue and PCB congener levels were determined and compared to levels in eggs collected from other breeding areas on Lake Maggiore and in a presumably less contaminated area on Lake Garda. Although Lake Garda eggs on average possessed a lower level of p,p'-DDE than Lake Maggiore eggs, they had significantly higher levels of PCBs and could not be used as a reference population for the measurement of eggshell thickness. Nevertheless, a negative linear relationship was found between p,p'-DDE concentration and eggshell thickness for eggs collected from both lakes, indicating a possible causal relationship. Testosterone and 17beta-estradiol concentrations were also determined for eggs collected from both lakes in 2004. Average concentrations of both hormones were the lowest in eggs from Lake Maggiore; however, the very high variability within broods did not result in any significant difference between the lakes.     

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.     

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.     

Depletion of selected polychlorinated biphenyl, dibenzodioxin, and dibenzofuran congeners in farmed rainbow trout (Oncorhynchus mykiss): a hint for safer fish farming

Farmed fish can be exposed to persistent organic contaminants--such as polychlorinated biphenyls (PCBs), dibenzodioxins (PCDDs), and dibenzofurans (PCDFs)--via feed, this eventually resulting in accumulation levels of health concern. To study the correlation between feed contamination, chemical accumulation in fish muscle (fillet), and chemical depletion, an all-vegetal base (or blank) feed was prepared and fortified with a commercial PCB mixture (Aroclor 1254) and six PCDD and PCDF congeners (namely, 2,3,7,8-T(4)CDD, 2,3,7,8-T(4)CDF, 1,2,3,7,8-P(5)CDD, 1,2,3,7,8-P(5)CDF, O(8)CDD, and O(8)CDF) to reproduce realistic low, medium, and high contamination levels. After a 1-month exposure, trout (Oncorhynchus mykiss) were fed with the blank feed and sacrificed every 0.5 months over a 3-month period from exposure end; fillet specimens were sampled at each time. In all groups, the average fish weight increased linearly through the observation period. The chemical diminishing patterns observed were due to the combined effect of clearance and growth dilution: for 10 PCB and four PCDD and PCDF congeners, patterns were described with an empirical one-compartment (fish muscle) model. The canonical pseudo-first-order kinetic equation used was also modified into the form C=[C(0)exp(-k(C)t)] (m(W)t+1)(-1) to distinguish between the contributions to depletion from clearance, exp(-k(C)t), and growth dilution, (m(W)t+1)(-1). Most mean clearance half-life (HL(C)) estimates appear to be greater than 4 months, in a number of cases reaching magnitudes well over 10 months or even negative, thus clearly indicating a non-negligible contribution from a second compartment. Based on means and their 95% confidence intervals, the depletion HL(D) estimates of the 14 selected congeners seem to be comprised between 1.2-3.4 and 1.0-5.0 months, respectively: these values, accounting for both clearance and growth dilution, provide an indication of the relevance of a blank feed as a management option to reduce the overall PCB, PCDD, and PCDF content in farmed trout. Due to a lack of bioaccumulation, O(8)CDD and O(8)CDF yielded no results for evaluation, whereas for many PCB congeners results were insufficient for empirical modelling.