Anthropogenic and natural influence on the PM(10) and PM(2.5) aerosol in Madrid (Spain). Analysis of high concentration episodes

Non-mineral carbon is the main component of PM10 and PM2.5 at an urban roadside site in Madrid accounting for more than 50% of the total bulk mass in winter pollution episodes. In these cases a 70-80% of the particle mass is anthropogenic. Particles of crustal/mineral origin contribute significantly to the observed PM10 concentrations, especially in spring and summer. They have also been found in the PM2.5 fraction although secondary particles are the next most important contributor in this size. Long-range transport particle episodes of Saharan dust significantly contribute to exceedence of the new daily limiting PM10 value in the urban network and at nearby rural background stations. This type of long-range transport event also influences PM2.5 concentrations. The crustal contribution can account for up to 67 and 53% of the PM10 and PM2.5 bulk mass in such cases.     

Evaluation of EU risk assessments existing chemicals (EC Regulation 793/93)

An evaluation was performed on the first group (41) of completed risk assessments for chemicals of the EU priority lists (Existing Chemicals; EC Regulation 793/93). The evaluation focussed on the conclusions of the risk assessments. The EU risk assessment process detected a high number of substances of concern. Furthermore priority chemicals may pose potential risks to the whole range of protection goals of the risk assessment. The predictability of the risk assessments for priority chemicals was investigated. Our a priori knowledge on possible risks of priority chemicals is found to be poor, especially for consumers. Both for environment and human health the potential risks were linked with a broad spectrum of use patterns. It is concluded that no industry category can in advance be excluded from performing risk assessments. For a great number of chemicals, additional testing was found to be needed to finalize the risk assessment. This evokes questions about the completeness of the current base-set, but also about the suitability of some of the submitted human health tests that should initially fulfil the base-set needs. The results of this evaluation are useful for ongoing discussions on risk assessment processes for chemicals.     

Results and evaluation of the first study of organochlorine contaminants (PCDDs, PCDFs, PCBs and DDTs), heavy metals and metalloids in birds from Baja California, México

Organochlorine compounds (OCs) including polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs) and 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (p-p'-DDE), heavy metals (Pb, Cd, Zn, Cu), and arsenic were measured in house sparrows (Passer domesticus) and common ground doves (Columbina passerina) from Baja California Sur, México. Concentrations of PCDD/Fs were low, with 21 pg/g for house sparrows, and 7.7 pg/g for common ground doves. Non-ortho-PCB concentrations in house sparrow and common ground doves were 58 and 254 pg/g, respectively, and are within the highest concentrations reported in species that are in the low levels of food webs. The major differences in organochlorine levels between species were found for ortho-PCBs and DDTs. ortho-PCB levels were higher in the seedeater species, whereas DDT levels were higher in the omnivorous species. Heavy metal levels were far below those associated with negative effects.     

Temporal trends of organochlorine contamination in Black Guillemots in Iceland from 1976 to 1996

The levels of several different persistent organochlorines (OCs) in Black Guillemots Cepphus grylle, collected during the summers of 1976-1996 at Breioafj?rour in W-Iceland, were investigated. The levels of about 40 different organochlorines (PCBs, DDTs, chlordanes, toxaphenes, HCH, HCB) were compared with respect to age, sex, fat content, and year of collection. The levels of PCBs correlated very closely with those of DDE, indicating long-range transport as the major source of these contaminants in Iceland, with the ratio PCBs/DDE mostly in the range of 2-5. Unlike the Gyrfalcon Falco rusticolus, the organochlorine levels did not seem to accumulate substantially with age, neither in males nor females. The variation in the levels of OCs at the age of 2 years was even greater than the variation in OC levels over an age range of 12 years. In immature birds the levels of PCBs, DDE, HCB and beta-HCH declined very slowly (T(1/2) from 12 to 20 years) over the years 1976-1996, whereas the levels of alpha-HCH and p,p'-DDT declined much faster. The levels of trans-nonachlor, alpha-chlordane, gamma-chlordane, oxychlordane, and toxaphene did not correlate with the year of collection. As the Black Guillemot is mostly a resident seabird, feeding mainly on small fish and invertebrates, this investigation should give a good indication of the temporal trends of organochlorine pollution at Breioafj?rour, Iceland, during this 20 year period and is likely to reflect baseline trends in the marine environment of the North-Atlantic Ocean.     

Treatment of chlorinated solvents by TiO2 photocatalysis and photo-Fenton: influence of operating conditions in a solar pilot plant

Titanium dioxide photocatalysis (using 20 0mg l(-1) of TiO2), under aerobic and anaerobic conditions, and photo-Fenton (2 and 56 mg l(-1) iron) were applied to the treatment of different NBCS (non-biodegradable chlorinated solvents), such as dichloroethane, dichloromethane and trichloromethane dissolved in water at 50 mg l(-1). All the tests were performed in a 35-l solar pilot plant with compound parabolic collectors (CPCs) under natural illumination. The two solar treatments were compared with attention to chloride release and TOC mineralisation, as the main parameters. Photo-Fenton was found to be the more appropriate treatment for these compounds, assuming volatilisation as a drawback of photocatalytic degradation of NBCS dissolved in water. In this context, several operating parameters related to NBCS degradation, e.g., treatment time, temperature, hydrogen peroxide consumption and volatility of parent compounds are discussed. The correct choice of operating conditions can very often diminish the problem of volatilisation during treatment.     

Monitoring of polychlorinated biphenyls in Belgian human adipose tissue samples

Polychlorinated biphenyls (PCBs) were monitored in Belgian human adipose tissue samples from deceased individuals (n=100). Their mean age was 52, ranging from 2 to 91 years. There were 57 men and 43 women. Other known variables were date of autopsy and place of residence. No information about diet or occupation was available. The seven marker congeners PCB 28, 52, 101, 118, 138, 153 and 180 were analysed in the samples with a GC-MS/MS method validated according to Commission Decision 2002/657/EC. Extracted fat was cleaned-up over a glass column filled with n-hexane, acid silica, deactivated alumina and anhydrous sodium sulfate. The whole procedure was subjected to a rigorous quality control programme with retention times, ion chromatograms and intensity ratios of the monitored product ions as identification criteria. The total PCB concentration ranged between 10 and 1640 ng g-1 fat, with a mean value of 658 ng g-1 fat. In the age groups of 0-9 (n=1), 10-19 (n=4), 20-29 (n=11), 30-39 (n=13), 40-49 (n=15), 50-59 (n=14), 60-69 (n=14), 70-79 (n=20), 80-89 (n=6) and 90-99 (n=2), the mean total PCB concentrations were 10, 134, 253, 445, 557, 687, 807, 962, 959, and 1191 ng g-1 fat, respectively. So, there was an increase of PCB body burden with age. For the male subjects (n=57; mean age of 53) the mean total PCB concentration was 633 ng g-1 fat. For the female subjects (n=43; mean age of 52) it was 690 ng g-1 fat. There was no significant sex-related difference in the concentrations of marker PCBs.     

Using thermal units for estimating critical period of weed competition in off-season maize crop

Brazilian off-season maize production is characterized by low yield due to several factors, such as climate variability and inadequate management practices, specifically weed management. Thus, the goal of this study was to determinate the critical period of weed competition in off-season maize (Zea mays L.) crop using thermal units or growing degree days (GDD) approach to characterize crop growth and development. The study was carried out in experimental area of the University of S?o Paulo, Brazil, with weed control (C), as well as seven coexistence periods, 2, 4, 6, 8, and 12 leaves, flowering, and all crop cycle; fourteen treatments were done. Climate data were obtained from a weather station located close to the experimental area. To determine the critical period for weed control (CPWC) logistic models were fitted to yield data obtained in both W and C, as a function of GDD. For an arbitrary maximum yield loss fixed in 2.5%, the CPWC was found between 301 and 484 GDD (7-8 leaves). Also, when the arbitrary loss yield was fixed in 5 and 10%, the period before interference (PBI) was higher than the critical weed-free period (CWFP), suggesting that the weeds control can be done with only one application, between 144 and 410 GDD and 131 and 444 GDD (3-8 leaves), respectively. The GDD approach to characterize crop growth and development was successfully used to determine the critical period of weeds control in maize sown off-season. Further works will be necessary to better characterize the interaction and complexity of maize sown off-season with weeds. However, these results are encouraging because the possibility of the results to be extrapolated and because the potential of the method on providing important results to researchers, specifically crop modelers.     

Reduction of silver solubility by humic acid and thiol ligands during acanthite (beta-Ag2S) dissolution

Precipitation of highly insoluble metal sulfide minerals like acanthite (beta-Ag2S) or red cinnabar (HgS) is in principle an effective means to reduce metal availability and toxicity in contaminated soils. Unfortunately, experiments have shown that red cinnabar may be solubilized in the presence of dissolved organic matter or thiol ligands. To determine whether the same applies to acanthite, a laboratory synthesized beta-Ag2S mineral was incubated for up to 3 weeks in the presence of KNO3, dissolved humic acids, cysteine, methionine and thiosulfate. XPS analysis identified Ag2O (52%), Ag2SO4 (8%) and Ag2S (40%) on the particle surfaces. Ag was released into solution in the presence of KNO3 and methionine, presumably from mixed-oxidation surface layers. Contrary to earlier results with cinnabar, however, humic acids reduced Ag concentrations in solution by about 75%, and cysteine and thiosulfate, each containing a free -SH functional group, almost completely suppressed Ag release into solution.     

Biosorption of water-soluble dyes on magnetically modified Saccharomyces cerevisiae subsp. uvarum cells

Brewer's yeast (bottom yeast, Saccharomyces cerevisiae subsp. uvarum) cells were magnetically modified using water based magnetic fluid stabilized with perchloric acid. Magnetically modified yeast cells efficiently adsorbed various water soluble dyes. The dyes adsorption can be described by the Langmuir adsorption model. The maximum adsorption capacity of the magnetic cells differed substantially for individual dyes; the highest value was found for aniline blue (approx. 220 mg per g of dried magnetic adsorbent).     

The relationship between surface adsorption and the hydrolysis of amitraz in anionic surfactant solutions

The adsorption of amitraz to various adsorbents was studied in terms of the amount and rate of adsorption and the effect that adsorption had on the stability of amitraz in an aqueous environment. Adsorption results showed that in terms of their ability to adsorb amitraz from solution the adsorbents tested in this study can be ordered as follows: coarse carbon > cation exchange resin > or = anion exchange resin > fine carbon. Amitraz was not adsorbed on sand and potassium oxihumate. Adding sodium lauryl sulfate and potassium oxihumate to aqueous suspensions of suspended adsorbents containing adsorbed amitraz showed that both these anionic surfactants significantly increased the hydrolysis rate because the half-lives for amitraz was reduced from 27 days for a suspension to only 8 hours for amitraz adsorbed to a cation exchange resin and suspended in an aqueous buffer pH 5.8 containing 0.5% of the anionic surfactant sodium lauryl sulfate and 12 hours when 1% potassium oxihumate was added.