Comprehensive study on dioxin contents in binder and anti-caking agent feed additives

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were determined in some additives widely employed as binder and anti-caking agents in feedstuffs, such as kaolin, bentonite, zeolite, etc. with an special attention on sepiolite samples. Owing to their physico-chemical properties, the little information of these materials reported in the literature, the variability of PCDDs/PCDFs found in a preliminary evaluation and the absence of reference materials highlighted further research needed. Therefore, an extensive study on the analytical procedures based on the classical methods was performed with sepiolite samples. The study includes evaluation of reproducibility and repeatibility. To this end, a series of intra-day and nine inter-day analysis were made. The methodolgy was also assessed against the sample size and series of 12.5, 25, 37.5 and 50 g were analyzed. In all cases, the results confirmed good correlation with the parameters evaluated.     

Decomposition of hazardous organic materials in the solidification/stabilization process using catalytic-activated carbon

The application of a catalytic-activated carbon to the solidification/stabilization (S/S) process for immobilization of phenol and 2-chlorophenol and catalytic decomposition was investigated. The effect of the catalytic-activated carbon, in amounts of 0.25-1% (by dry sand wt.), on the leaching of phenol and 2-chlorophenol was studied. H2O2 was added as a source of oxygen in the amounts of 1 or 5%, with respect to liquid solution weight. Toxicity characteristic leaching procedure (TCLP) leaching tests showed that adding the catalytic-activated carbon to the S/S matrix significantly reduced the leachability of both phenol and 2-chlorophenol. Only trace amounts of phenol were found in the leaching solution, while the concentration of 2-chlorophenol was below the detection limit of the gas chromatography (GC). Without addition of the catalytic-activated carbon, 87% of the phenol and 92% of the 2-chlorophenol leached. Additional tests on TCLP leachate solutions using GC-mass spectrometry indicated the existence of simple, less hazardous, hydrocarbons, including alcohol. Catalytic-activated carbons treated with phenol in the presence of H2O2 were also analyzed using time of flight-secondary ion mass spectroscopy (TOF-SIMS). Results indicate that the phenol aromatic ring was broken by the catalytic reaction.     

Pesticides in surface water,sediment, and rainfall of the northeastern Pantanal basin,Brazil

Within the last 25 years an intensive agriculture has developed in the highland regions of Mato Grosso state (Brazil), which involves frequent pesticide use in highly mechanized cash-crop cultures. To provide information on pesticide distribution and dynamics in the northeastern Pantanal basin (located in southern Mato Grosso), we monitored 29 pesticides and 3 metabolites in surface water, sediment, and rainwater of the study area during the main application season. In environmental samples, 19 pesticides and 3 metabolites were detected in measurable quantities, resulting in at least one pesticide detection in 68% of surface water samples (n = 139), 62% of sediment samples (n = 26), and 87% of rainwater samples (n = 91). Surface water samples were most frequently contaminated by endosulfan compounds (alpha-, beta-, -sulfate), ametryn, metolachlor, and metribuzin, although in low (< 0.1 microgram L-1) concentrations. Sediment samples exhibited concentrations up to 4.5 micrograms kg-1 of p,p'-DDT, p,p'-DDE, endosulfan-sulfate, beta-endosulfan, and ametryn. In contrast, rainwater was polluted with substantial amounts of endosulfan, alachlor, metolachlor, trifluralin, monocrotofos, and profenofos (maximum concentrations = 0.3 to 2.3 micrograms L-1) in the highlands. Lowland rainwater samples taken 75 km from the next application area contained 5- to 10-fold lower mean pesticide concentration than in the highlands. Cumulative deposition rates of the pesticide sum within the study period ranged from 423 micrograms m-2 in the highlands to 14 micrograms m-2 in the lowlands. The atmospheric input of pesticides to ecosystems seemed to be of higher relevance in the tropical study area than known from temperate regions.     

Fate of pesticides in tropical soils of Brazil under field conditions

The potential of pesticides for nonpoint ground water pollution depends on their dissipation and leaching behavior in soils. We investigated the fate of 10 pesticides in two tropical soils of contrasting texture in the Brazilian Cerrado region near Cuiabá during an 80-d period, employing topsoil dissipation studies, soil core analyses, and lysimeter experiments. Dissipation of pesticides was rapid, with field half-lives ranging from 0.8 to 20 d in Ustox and 0.6 to 11.8 d in Psamments soils. Soil core analyses showed progressive leaching of polar pesticides in Psamments, whereas in Ustox pesticides were rapidly transported to 40 cm soil depth regardless of their sorption properties, suggesting that leaching was caused by preferential flow. In lysimeter experiments (35 cm soil depth), cumulative leaching was generally low, with < or = 0.02% and < or = 0.19% of the applied amounts leached in Ustox and Psamments, respectively. In both soils, all pesticides but the pyrethroids were detected in percolate at 35 cm soil depth within the first 6 d after application. Cumulative efflux and mean concentrations of pesticides in percolate were dosely correlated with their Groundwater Ubiquity Score (GUS). The presence of alachlor (2-chloro-2', 6'-diethyl-N-methoxymethylacetanilide), atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine), metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide], simazine [2-chloro-4,6-bis(ethylamino)-1,3,5-triazine], and trifluralin (2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline) throughout the soil profile and in percolate of wick lysimeters at 95 cm soil depth indicated that a nonpoint pollution of ground water resources in tropical Brazil cannot be ruled out for these substances.     

Metal pollution in Spanish terrestrial ecosystems during the twentieth century

We show here additional biological evidence of the alteration in global biogeochemistry by human activities during the twentieth century. The mineral concentration of herbarium specimens of 24 species of vascular plants and three species of bryophytes collected in North and East regions of Spain have substantially changed throughout the twentieth century. While V, a proxy tracer of oil pollution, exponentially increased in the last decades, other metals such as Cr, Ba, Sr, Al, Fe, Pb, Cd and Ti increased up to 1960-1970 and started to decrease in 1985-1995, when environmental legal regulations started to be effective. Multivariate principal component analysis showed an overall change in plant elemental concentrations throughout the different decades of the century and a clear separation of vascular plants and bryophytes. Likely important consequences for ecosystem structure and functioning and even for human health may be expected from these changes in mineral concentration.     

Sources, distribution and behaviour of methyl tert-butyl ether (MTBE) in the Tamar Estuary, UK

Negligible information is currently available concerning levels of the fuel additive methyl tert-butyl ether (MTBE) in European estuaries or coastal environments. MTBE was measured at selected potentially contaminated harbours and marinas, and throughout an axial transect of the Tamar Estuary, UK. Headspace solid-phase microextraction was used in combination with GC-MS for its determination. MTBE was detected in water samples from all stations at concentrations ranging from a few ng/l to a maximum of 194 ng/l (in a semi-enclosed harbour). Elevated levels were generally associated with motor vehicle and boating activities. The Tamar road and rail bridges provided a major input to the lower estuary, downstream of which conservative mixing appeared depressed, probably through volatilisation and possibly through salting-out. The selected analytical system (using a Carboxen/PDMS fiber) proved both rapid and highly sensitive (with a detection limit of 6 ng/l). During method development, salinity was shown to have a major influence in controlling the extraction efficiency and it was found necessary to adjust salinity in all samples (to 75% saturation) prior to extraction. From these tests, we (for the first time) estimated the Setschenow ("salting-out") constant of MTBE to be 0.11 l/mol.     

Trace element accumulation in the moss Hypnum cupressiforme Hedw. and the trees Quercus ilex L. and Pinus halepensis Mill. in Catalonia

We studied trace element accumulation in the moss Hypnum cupressiforme and the widely distributed Mediterranean trees Quercus ilex and Pinus halepensis located at increasing distances from the Barcelona Metropolitan Area. Hypnum cupressiforme, Quercus ilex and, to a somewhat lesser extent, Pinus halepensis, have proved to be adequate as possible accumulative monitoring species in relation to trace elements pollution. No significant effects of crown orientation were found. One-year old leaves generally accumulated more trace elements than current-year leaves. All the studied trace elements showed greatest concentrations in the Barcelona Metropolitan Area, with lead, cadmium and arsenic concentrations being especially high. In general, trace element concentrations in biomass were similar or higher than the values reported from other Mediterranean urban areas of Europe. The top soil-layer concentrations were also higher in the Barcelona Metropolitan Area indicating the existence of mechanisms of atmospheric deposition and/or concentration in the soil. The lower values of Pb of airborne origin relative to other elements such as Cd, Cu, Zn and Sb suggest that traffic exhausts are not the only important focus of pollutants in this area. The results of biomass concentrations and of enrichment factor of biomasses respect to bedrock and soils show that atmospheric inputs account for the higher trace element concentrations in the Barcelona Metropolitan Area.     

Improvements in dioxin abatement strategies at a municipal waste management plant in Barcelona

This study presents the results of a dioxin abatement programme undertaken in the municipal waste incineration plant of Montcada i Reixac (Barcelona, Spain) after the replacement of an obsolete air cleaning device by a new flue gas treatment system. A number of sampling campaigns were conducted with the aim of characterising stack gas emission levels of polychlorinated dibenzo-p-dioxins (PCDDs)/polychlorinated dibenzofurans (PCDFs) and to evaluate initial specifications of dioxin stack gas emission values below 0.1 ng I-TEQ/Nm(3). Preliminary results revealed levels between 44 and 111 ng I-TEQ/Nm(3) when the gas-cleaning system consisted only of an old electrostatic precipitator (ESP). Decreased levels around 15 ng I-TEQ/Nm(3) were observed when the semi-dry scrubber began to operate and the ESP was switched off. Again, remarkable dioxin removal was observed after the installation of the fabric filter and levels around 0.3-0.4 ng I-TEQ/Nm(3) were soon achieved. Nevertheless, the limit of 0.1 ng I-TEQ/Nm(3) was reached by additional injection of activated carbon which helped to lower PCDD/PCDF levels to around 0.036 ng I-TEQ/Nm(3). The results also demonstrated a significant change in the dioxin distribution present in combustion-derived materials (stack gas emission, bottom ash and solid waste from gas treatment). The major dioxin fraction was found in gaseous matrices before the flue gas control system was upgraded. After this step, the major dioxin fraction content was observed in solid waste from gas treatment.     

Evaluation of Organochlorine Compounds (PCDDs,PCDFs, PCBs and DDTs) in Two Raptor Species Inhabiting a Mediterranean Island in Spain (8 pp)

Background Species that are at high levels of the food web have often been used as bioindicators to evaluate the presence of persistent contaminants in ecosystems. Most of these species are long-lived, so pollutant burdens may be integrated in some complex way over time. This makes them particularly sensitive to deleterious effects of Persistent Organic Pollutants (POPs). Birds have been suggested as useful organisms for monitoring pollutant levels. Traditionally such studies have been carried out with raptors such as osprey (Pandion haliaetus), peregrine falcon (Falco peregrinus), bald eagle (Haliaetus leucocephalus), etc. In this paper we present the results of a monitoring study conducted on two raptor species, osprey (Pandion haliaetus) and red kite (Milvus milvus), inhabiting a Mediterranean island (Menorca, Spain). These two species have different feeding habits; ospreys prey on fish and red kites feed on terrestrial species. This study constitutes a good opportunity to investigate if differences in feeding habits (aquatic vs. terrestrial) influences the contaminants pattern in two species inhabiting the same area. Methods The study was conducted in a non-destructive way, using only failed eggs, to avoid the damage of the population stability. Eggs were collected during the period 1994–2000. The contaminants examined were dichlorodiphenyltrichloroethanes (DDTs, including DDT and its main metabolite, DDE), polychlorinated biphenyls (PCBs), including ortho PCBs (PCBs with at least one Chlorine atom in the ortho position): #28, 52, 95, 101, 123+149, 118, 114, 153, 132+105, 138, 167, 156, 157, 180, 170, 189, 194; and non ortho PCBs (PCBs with no Chlorine atom in the ortho position): #77, 126, 169 and all the polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) with Chlorine atoms at the 2,3,7 and 8 position (2,3,7,8-substituted PCDDs and PCDFs). The analysis of organochlorine compounds was performed using a sample treatment based on a Solid Phase Matrix Dispersion procedure. Ortho PCBs and DDTs were determined by HRGC-μECD; non ortho PCBs and PCDD/Fs were determined by HRGC-HRMS. Results and Discussion The sum of the ortho PCB congeners analysed ranged from 0.94 to 15.03 μg/g wet weight (ww) for ospreys and from 1.0 to 11.2 μg/g ww for red kites. In both species, PCB congeners #153, #138 and #180 accounted about 75% to total ortho PCB concentrations. Regarding non ortho PCBs, for ospreys, concentrations ranged from 0.16 to 1.39 ng/g wet weight (ww) and for red kites from 0.12 to 0.51 ng/g ww, being congener #126 the most abundant. Concerning DDTs, concentration for ospreys ranged from 0.07 to 1.03 μg/g ww; and for red kites ranged from 0.90 to 2.10 μg/g ww, representing DDE more than 95% of the total DDTs, which proves a past use of DDT in the study area. Differences in contaminant levels between species are probably associated to feeding habits. The fish-eating species presents the highest PCB levels, whereas the terrestrial species exhibits the highest DDT levels. PCDD/Fs in ospreys were in the range 2.6–14.2 pg/g ww, while in red kites the range was slightly wider (22.2–43.2 pg/g ww), being PCDDs the major contributors in black kites. Ospreys had PCDDs similar to PCDF concentrations. PCDD/F profiles were mostly influenced by OCDD in both species. Non ortho PCBs were the major contributors to calculated Toxic Equivalent Quantity (TEQs) in both species. Conclusion In both species studied, ortho-PCBs could represent a problem of concern since 57% of the eggs exhibited levels higher than 4 μg/g ww, reported as the level that could cause reduced hatchability, embryo mortality, and deformities in birds. Recommendations and Outlook Results found in this study suggest that a more detailed study to clear up possible deleterious effects of PCBs on the bird populations studied here should be done. Section Editor: Prof. Dr. Paola Gramatica (paola.gramatica@uninsubria.it)