Accumulating pollutants in conifer needles on an Atlantic island - a case study with Pinus canariensis on Tenerife, Canary Islands

Concentrations of potential pollutant elements Na, Cl, and S were investigated in needles of Pinus canariensis grown at 55 field plots in Tenerife. Microelement concentrations (including heavy metals) were measured at a subset of 18 plots. Na and Cl concentrations were high at low elevations (up to 8 mg g(-1) Cl and 5.5 mg g(-1) Na). Na/Cl ratio close to standard seawater indicated sea spray influence up to 1200 m a.s.l. Only at few plots, sulphur concentrations indicated possible pollutant impact. Cluster and correlation analyses identified a related group of V, As, Cr, Fe, Mo, Ni, Cu, Pb, and Al, possibly related to traffic exhaust aggregated with soil particles. Mainly north-eastern, lower elevated plots were exposed to those immissions, but metal concentrations were generally low compared to data from other studies. In conclusion, seawater and soil particles explained most of the element distribution pattern in pine needles in Tenerife, but strong indications for some effect of local sources of air pollutants were detected.     

Dietary exposure to PCDD/PCDFs by individuals living near a hazardous waste incinerator in Catalonia, Spain: temporal trend

The levels of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) were measured in foodstuffs randomly acquired in July 2006 in various locations of Tarragona County (Catalonia, Spain), which are near a hazardous waste incinerator (HWI). A total of 35 composite samples, belonging to various food groups (vegetables, pulses, cereals, fruits, fish and seafood, meat and meat products, eggs, milk, dairy products, and oils and fats) were analyzed by HRGC/HRMS. The dietary intake of PCDD/PCDFs was subsequently determined and compared with a previous survey performed in 2002. For calculations, recent data on consumption of the selected food items were used. Total dietary intake of PCDD/PCDFs for the general population of Tarragona County was estimated to be 27.81 pg WHO-TEQ/day, value notably lower than that found in the 2002 study, 63.80 pg WHO-TEQ/day. Fish and seafood (28%), oils and fats (22%), eggs (17%), and dairy products (11%) were the most important contributors to this intake, while pulses (1%), milk (2%), vegetables (3%) and fruits (3%) showed the lowest contribution to total WHO-TEQ. The current PCDD/PCDF intake is also considerably lower than the intake estimated in 1998 for the population of the same geographical area, 210.1 pg I-TEQ/day, when a baseline study was carried out during the construction of the HWI. The present intake is also compared with the dietary intakes of PCDD/PCDFs recently (2006-2007) reported for a number of regions and countries.     

PCDD/F concentrations in milk of nonoccupationally exposed women living in southern Catalonia, Spain

Concentrations of 17 toxic 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) have been determined in pooled samples of breast milk from 15 mothers living in two residential areas (Tarragona downtown and an industrial area) in the vicinity of a new hazardous waste incinerator (HWI), now under construction in Tarragona (southern Catalonia, Spain). PCDD/Fs in human milk samples ranged between 5.9 and 17.1 pg I-TEQ/g fat (162-498 pg I-TEQ/l), with a mean value of 11.8 pg I-TEQ/g fat (310.8 pg I-TEQ/l). The percentages of fat ranged between 1.53 and 3.52. Although PCDD/F levels in milk from mothers living in the industrial area were found to be slightly higher than those observed in women living Tarragona downtown, most differences did not reach the level of statistical significance. In general terms, PCDD/F concentrations in human milk (pooled) samples of mothers living in the area of Tarragona are similar or lower than those previously reported for most industrialized countries.     

The use of olive-mill waste compost to promote the plant vegetation cover in a trace-element-contaminated soil

The applicability of a mature compost as a soil amendment to promote the growth of native species for the phytorestoration of a mine-affected soil from a semi-arid area (SE Spain), contaminated with trace elements (As, Cd, Cu, Mn, Pb and Zn), was evaluated in a 2-year field experiment. The effects of an inorganic fertiliser were also determined for comparison. Bituminaria bituminosa was the selected native plant since it is a leguminous species adapted to the particular local pedoclimatic conditions. Compost addition increased total organic-C concentrations in soil with respect to the control and fertiliser treatments, maintained elevated available P concentrations throughout the duration of the experiment and stimulated soil microbial biomass, while trace elements extractability in the soil was rather low due to the calcareous nature of the soil and almost unaltered in the different treatments. Tissue concentrations of P and K in B. bituminosa increased after the addition of compost, associated with growth stimulation. Leaf Cu concentration was also increased by the amendments, although overall the trace elements concentrations can be considered non-toxic. In addition, the spontaneous colonisation of the plots by a total of 29 species of 15 different families at the end of the experiment produced a greater vegetation cover, especially in plots amended with compost. Therefore, the use of compost as a soil amendment appears to be useful for the promotion of a vegetation cover and the phytostabilisation of moderately contaminated soils under semi-arid conditions.     

Baseline levels of bioaerosols and volatile organic compounds around a municipal waste incinerator prior to the construction of a mechanical-biological treatment plant

New waste management programs are currently aimed at developing alternative treatment technologies such as mechanical–biological treatment (MBT) and composting plants. However, there is still a high uncertainty concerning the chemical and microbiological risks for human health, not only for workers of these facilities, but also for the population living in the neighborhood. A new MBT plant is planned to be constructed adjacently to a municipal solid waste incinerator (MSWI) in Tarragona (Catalonia, Spain). In order to evaluate its potential impact and to differentiate the impacts of MSWI from those of the MBT when the latter is operative, a pre-operational survey was initiated by determining the concentrations of 20 volatile organic compounds (VOCs) and bioaerosols (total bacteria, Gram-negative bacteria, fungi and Aspergillus fumigatus) in airborne samples around the MSWI. The results indicated that the current concentrations of bioaerosols (ranges: 382–3882, 18–790, 44–926, and <1–7 CFU/m³ for fungi at 25 °C, fungi at 37 °C, total bacteria, and Gram-negative bacteria, respectively) and VOCs (ranging from 0.9 to 121.2 μg/m³) are very low in comparison to reported levels in indoor and outdoor air in composting and MBT plants, as well in urban and industrial zones. With the exception of total bacteria, no correlations were observed between the environmental concentrations of biological agents and the direction/distance from the facility. However, total bacteria presented significantly higher levels downwind. Moreover, a non-significant increase of VOCs was detected in sites closer to the incinerator, which means that the MSWI could have a very minor impact on the surrounding environment.     

PCDD/F and metal concentrations in soil and herbage samples collected in the vicinity of a cement plant

Juvenoids are biologically active compounds, of relatively low toxicity to humans, that efficiently inhibit the fertility of insects. However, little attention has been paid to the stability and toxicity of products that may be generated by their biodegradation in the ecosystem. This study describes a simple comparison of the toxicity of the active compound and its degradation products generated by aerobic soil microbial isolates. Surprisingly we have found that toxicity of a biologically active carbamate juvenoid N-[2-[4-(2,2-ethylenedioxy-1-cyclohexylmethyl)-phenoxylethyl]carbamate (W328) was comparable with that of 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT). The toxic effect was evaluated using the determination of the ATP/ADP content and viability of HeLa S3 cells exposed to various concentrations of the chemicals tested for various durations. DDT was used as a reference compound. Its toxicity was compared with two juvenile hormone analogs. The original compound, W328, was found to be the most toxic. The major product (W329) generated both by yeast isolates and the mixture of moulds lost its activity on reproduction of the tested insect. Its toxicity towards human cells was also decreased. Another two W328 degradation HPLC fractions exhibited significantly reduced toxicity compared to W328.     

Patterns of PCDDs and PCDFs in human milk and food and their characterization by artificial neural networks

Artificial neural network (ANN) has been recently introduced as a tool for data analysis. In this study, Kohonen's self-organizing maps (SOMs), a special type of neural network, were applied to a set of PCDD/PCDF concentrations found in 54 human milk and 83 food samples, which were collected in a number of countries all over the world. Data were obtained from the scientific literature. The purpose of the study was to find a potential relationship between PCDD/PCDF congener profiles in human milk and the dietary habits of the different countries in which samples were collected. The comparison of the SOM component planes for human milk and foodstuffs indicates that those countries with a greater fish consumption show also higher PCDD/PCDF concentrations in human milk. SOMs enable both the visualization of sample units and the visualization of congener distribution.     

Multi-compartmental environmental surveillance of a petrochemical area: levels of micropollutants

Since 2002, the chemical/petrochemical industrial zone of Tarragona County (Catalonia, Spain) is being annually monitored. As part of the environmental surveillance program, in this study the levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), polycyclic aromatic hydrocarbons (PAHs), and metals (As, Cd, Cr, Hg, Mn, Pb and V) were determined in soil and vegetation samples collected in 4 areas of Tarragona County (chemical, petrochemical, urban/residential, and unpolluted). Moreover, the airborne concentrations of the same micropollutants were determined in each area. In soil samples, significant higher levels of PCNs and higher concentrations of PCDD/Fs and PAHs were found in the urban zone. PCDD/F levels in vegetation samples significantly decreased from 2002. The concentrations of Cr in soil samples, as well as V levels in vegetation samples collected in the vicinity of an oil refinery were significantly higher than those found in the unpolluted zones. A significant and progressive increase in V concentrations was also noted. The current results clearly indicate that the petrochemical industry is still being an important focus of inorganic pollution for the surrounding environment. In air, the higher amount of the 7 carcinogenic PAHs suggests a relatively greater impact on the petrochemical and urban areas. The temporal trend of the global pollution was also studied an Integral Risk Index was applied.     

Weathering patinas on the medieval (S. XIV) stained glass windows of the Pedralbes Monastery (Barcelona, Spain)

Background, aim, and scope  The first step in the restoration of a medieval stained glass window is the evaluation of its degree of degradation. This implies the study of the chemical composition of the stained glass as well as the new mineral phases developed on its surface (patinas). Patinas are clearly related to glass composition, time, environmental conditions, microenvironments developed in local zones, bioactivity, physical and chemical factors, etc. This study was carried out on patinas developed in selected Na-rich stained glass of the Santa Maria de Pedralbes Monastery (Barcelona, Spain). The location of this monument in the city (about 5 km from the shoreline and close to the Collserola hill flank) helped to determine the environmental conditions in which patinas developed. The aim of our study was to characterize the patinas formed on the surface of the selected glass of this monastery in order to understand the role of the chemical composition of the original glass (Na-rich) as well as the environmental conditions in which they developed. Materials and methods  Powdered samples of two different color-type patinas (ochre-orange and brownish) were collected in the external and internal parts of the stained glass windows of the Prebystery and Chapter House of the Pedralbes Monastery by using a precision (odontological) drill. These patinas were subsequently analyzed by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). Results  XRD analyses evidenced the presence of sulfates (gypsum and thenardite), calcite, Ca-oxalates (whewellite and weddellite), and quartz forming part of the patinas. Although these mineral phases can be found in both color-type patinas, whewellite and thenardite are more common in the ochre-orange patinas. The results obtained were validated by the FTIR measurements. It has been observed, when thenardite is present, that gypsum occurs as traces. Thenardite is in most of the cases associated with whewellite and mainly occurs in the internal parts of the glass. In contrast, weddellite is limited to the absence of thenardite and whewellite and to the external parts of the stained glass. Quartz is present in all the patinas independent of their location and color. Calcite also occurs in many samples. It appears in both color-type patinas and, in some cases, is associated to the presence of weddellite but not to whewellite and/or thenardite. Discussion  Glass composition together with environmental conditions and location of the patinas (internal or external parts of the stained glass window), as well as the provenance of the glass within the monastery, are the main factors that define the development of the new mineral phases. Moreover, the action of microorganisms, when present, can also strongly influence the development of some mineral phases. For example, the formation of calcite in the external parts of the stained glass (associated with the presence of oxalates) is related to the action of microorganisms. When calcite is formed in the internal parts of the glass and it is not associated with the presence of Ca-oxalates, an inorganic origin can be invoked. The presence of weddellite requires a very humid microenvironment with very little exposure to sunlight. In fact, this mineral phase has only been observed in the external parts of some glass located in the humid and shady side of the monastery. Whewellite (which only appears in the internal parts) needs a low degree of relative humidity. It has been observed that sulfur precipitating in basically one mineral phase (thenardite or gypsum) depends on the microenvironmental conditions of the moment and the glass composition. When thenardite occurs, it can be maintained that the original glass is of Na composition. The occurrence of quartz in all samples is interpreted as being due to the deposition of atmospheric particulate matter. The color of the patinas can be originated by different processes (presence of carotenes, organic pigmentation, atmospheric contamination, etc.). Conclusions  In the case of moderately weathered stained glass windows, the combination of XRD and FTIR techniques is very useful to obtain a fast preliminary evaluation of the degree of weathering of a stained glass window. The presence of specific mineral phases in the patina (e.g., thenardite) confirms the Na composition of the original stained glass. This is important since Na-rich glass underwent a lesser degree of weathering than K- or K-Ca-rich glass. However, their absence cannot preclude other possibilities. It has been extensively evidenced through time that environmental conditions play an important role on the formation of the different mineral phases which form part of the patinas. Recommendations and perspectives  The first step in the restoration of a stained glass window is the evaluation of the degree of deterioration of the glass. This evaluation includes a chemical analysis of the glass as well as a characterization of the patinas developed on their surfaces. The obtained results will be essential in order to define the best restoration practices to be followed.