Analysis of short-chain chlorinated paraffins: a discussion paper

Short-chain chlorinated paraffins are a class of organic compounds widely used in many industrial applications, extensively diffused into the environment, persistent, bioaccumulative, and toxic towards aquatic organisms. However, their study and monitoring in the environment are still limited. Because of the enormous number of positional isomers that characterise their mixtures, the analysis of this class of pollutants is very difficult to perform. Beside this, the lack of certified reference materials poses a problem for the assessment of the quality assurance/quality control of any analytical procedure. At present, the scientific community does not agree on any analytical reference method, although the monitoring of short-chain chlorinated paraffins has already started in order to comply with the Water Framework Directive of the European Union on water quality. In this paper the regulatory framework, in which chlorinated paraffins are included, and the status concerning their determination are summarized. The main analytical difficulties still existing are discussed, and the definition of a method-defined parameter as well as the development of a standardised method are suggested as a way to obtain comparable monitoring data.     

Contributions of deposited particles to pine needle polycyclic aromatic hydrocarbons

The contributions of deposited particles (P) to polycyclic aromatic hydrocarbon (PAH) levels in pine (Cedrus deodar) needles sampled from the Dalian region were evaluated by washing off the particles from pine needle surfaces. P values ranged from 4.4 +/- 2.2% for fluorene to 69.9 +/- 4.0% for indeno(1,2,3-cd)pyrene, and positively correlated with the logarithm of octanol-air partition coefficients (log K OA) of each PAH significantly. P and the total levels of 14 PAHs under study ( summation PAHs), that ranged from 490 to 3241 ng g(-1) dw (dry weight) with median value of 1521 ng g(-1) dw, were high for traffic areas, and low for residential or park areas, implying the significant contributions of PAHs in both gas and particle phases emitted by vehicles. However, PAH profiles in pine needles were not significantly altered by the washing, due to the low fractions (2-5%) of the 5- and 6-ring PAHs in summation PAHs. The high wind speed and frequently alternating wind directions in the Dalian spring could quicken the depuration processes of pine needle PAHs. Thus, the local meteorological conditions and source variations should be taken into account when using pine needles to implicate seasonal variations of atmospheric semi-volatile organic compounds.     

Risk assessment of contaminated sediments in river basins--theoretical considerations and pragmatic approach

In order to ensure chemical quality of river basins, measures as required in the Water Framework Directive will also have to address contaminated sediments with subsequent monitoring of their successful application. Financial resources need to be allocated as part of a river basin plan to those contaminated sites that pose the biggest risk to the river basin. In order to differentiate between areas with elevated contaminant levels ("areas of concern") and those sites from which contaminated sediments can become resuspended and transported with the river, affecting the water phase and downstream sites in the catchment ("areas of risk"), the dynamics of sediment and suspended matter need to come into focus. Hydrological data have to be combined with concentration of suspended matter and its contaminant concentration to allow assessment of particle bound contaminant load. Each of these kinds of data, however, are subject to uncertainties--e.g. due to natural variability, heterogeneity of the matrix, challenges during sampling and chemical analyses of the suspended matter. Considering these uncertainties throughout the traceability chains of data collection, use of different lines of evidence and tools like fuzzy logic will increase the confidence of potentially costly management decisions.     

Trends in the elemental composition of fine particulate matter in Santiago, Chile, from 1998 to 2003

Santiago, Chile, is one of the most polluted cities in South America. As a response, over the past 15 yr, numerous pollution reduction programs have been implemented by the environmental authority, Comisión Nacional del Medio Ambiente. This paper assesses the effectiveness of these interventions by examining the trends of fine particulate matter (PM(2.5)) and its associated elements. Daily fine particle filter samples were collected in Santiago at a downtown location from April 1998 through March 2003. Additionally, meteorological variables were measured continuously. Annual average concentrations of PM(2.5) decreased only marginally, from 41.8 microg/m3 for the 1998-1999 period to 35.4 microg/m3 for the 2002-2003 period. PM(2.5) concentrations exceeded the annual U.S. Environmental Protection Agency standard of 15 microg/m3. Also, approximately 20% of the daily samples exceeded the old standard of 65 microg/m3, whereas approximately half of the samples exceeded the new standard of 35 microg/m3 (effective in 2006). Mean PM(2.5) levels measured during the cold season (April through September) were three times higher than those measured in the warm season (October through March). Particulate mass and elemental concentration trends were investigated using regression models, controlling for year, month, weekday, wind speed, temperature, and relative humidity. The results showed significant decreases for Pb, Br, and S concentrations and minor but still significant decreases for Ni, Al, Si, Ca, and Fe. The larger decreases were associated with specific remediation policies implemented, including the removal of lead from gasoline, the reduction of sulfur levels in diesel fuel, and the introduction of natural gas. These results suggest that the pollution reduction programs, especially the ones related to transport, have been effective in reducing various important components of PM(2.5). However, particle mass and other associated element levels remain high, and it is thus imperative to continue the efforts to improve air quality, particularly focusing on industrial sources.     

Monitoring Water Quality and Quantity of National Watersheds in Turkey

National data from the hydrological network for 38 rivers out of 25 watersheds were used to detect spatial and temporal trends in water quality and quantity characteristics between 1995 and 2002. Assessment of water quality and quantity included flow rate, water temperature, pH, electrical conductivity, sodium adsorption rate, Na, K, Ca+Mg, CO₃, HCO₃, Cl, SO₄, and boron. Among the major ions assessed on a watershed basis, Turkish river waters are relatively high in Ca+Mg, Na and HCO₃, and low in K and CO₃. The watersheds in Turkey experienced a general trend of 16% decrease in flow rates between 1995 and 2002 at a mean annual rate of about 4 m³ s^?1, with a considerable spatial variation. Similarly, there appeared to be an increasing trend in river water temperature, at a mean annual rate of about 0.2°C. A substantial proportion of watersheds experienced an increase in pH, in particular, after 1997, with a maximum increase from 8.1 to 8.4 observed in Euphrates (P?R ² values in accounting for variations of pH and water temperature only. The findings of the study can provide a useful assessment of controls over water quality and quantity and assist in devising integrated and sustainable management practices for watersheds at the regional scale in Turkey.     

Active biomonitoring of heavy metal pollution using Rosa rugosa plants

The purpose of this work was to evaluate the quality of a rural area near Faenza (Italy) by using an active biomonitoring approach, i.e., by placing homogeneous individuals of the perennial shrub Rosa rugosa in different sites throughout the area. Further sites, within the city or its environs, were used for comparison. Soil and leaves of R. rugosa were analyzed for their heavy metal content. The total heavy metal pattern of leaves closely paralleled the pattern registered in soil, with the highest content (both in total and assimilable forms) at the site in the urban area, which is exposed to heavy traffic. Pollen quality (abortiveness and viability) was also tested as a potential indicator of pollution. Pollen abortiveness was strictly related to Pb levels in leaves, while viability was inversely related to leaf Cr content. Our results suggest that R. rugosa has the potential to be a good biomonitoring system.     

Fate of RDX and TNT in agronomic plants

Phytoremediation is of great interest to remediate soil contaminated with hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4,6-trinitrotoluene (TNT). The ability of 4 agronomic plants (maize, soybean, wheat and rice) to take up these explosives and their fate in plants were investigated. Plants were grown for 42 days on soil contaminated with [(14)C]RDX or [(14)C]TNT. Then, each part was analyzed for its radioactivity content and the percentage of bound and soluble residues was determined following extractions. Extracts were analyzed by radio-HPLC. More than 80% of uptaken RDX was translocated to aerial tissues, up to 64.5 mgg(-1) of RDX. By contrast, TNT was little translocated to leaves since less than 25% of uptaken TNT was accumulated in aerial parts. Concentrations of TNT residues were 20 times lower than for RDX uptake. TNT was highly metabolized to bound residues (more than 50% of radioactivity) whereas RDX was mainly found in its parent form in aerial parts.     

Results of the monitoring program of pesticide residues in organic food of plant origin in Lombardy (Italy)

Organic agriculture, with its restrictions on the use of synthetic chemical inputs, seems to offer a low-residue alternative to conventional methods. In Europe, the Council Regulation n. 2092/91/EEC regulates the production and trade of organic products and foodstuffs; national and regional legislation in Italy gives specific guidance on the surveillance of organic agriculture. However, monitoring of specific chemical residues in organic foodstuffs is part of the regular controls on food, aiming to safeguard consumer's health. Monitoring programs are coordinated at the national level by the Ministry of Health and at local level by Regional authorities. In Lombardy, in accordance with the provisions of the General Directorate of Health of the Region and under the supervision of the 15 Local Health Units, a monitoring program of pesticide residues in food of plant origin is undertaken every year. The International Centre for Pesticides and Health Risk Prevention (ICPS), on behalf of the General Directorate of Health of the Region of Lombardy, has been collecting and elaborating the data resulting from the analysis of food samples, carried out by the local laboratories. During the period 2002-2005, a total of 3508 samples food of plant origin were analyzed for pesticide residues, among which were 266 samples of organic farming products. Commodities were classified into groups (citrus fruits, legumes, vegetables, potatoes, processed products, cereals, and fruit other than citrus) and the outcomes of the analyses were reported by year, origin of the sample and presence/absence of pesticide residues. Results showed that the vast majority of organic farming products were in conformity with the relevant legislation and did not contain detectable pesticide residues. A limited amount of samples had residues at concentration below the Maximum Residue Limit (MRL). Only in one sample the residue level was above the MRL, however it did not pose a concern for public health, as demonstrated by the outcomes of dietary risk assessment. Organic fruits and vegetables can be expected to contain fewer agrochemical residues than conventionally grown alternatives. There is a widespread belief that organic agriculture products are safer and healthier than conventional foods. It is difficult to come to conclusions, but what should be made clear to the consumer is that "organic" does not automatically equal "safe". In the absence of adequate comparative data, additional studies in this area of research are required.     

Influence of humic fractions on retention of isoproturon residues in two Moroccan soils

The influence of different fractions of soil organic matter on the retention of the herbicide isoproturon (IPU) has been evaluated. Water and methanol extractable residues of (14)C labeled isoproturon have been determined in two Moroccan soils by beta -counting-liquid chromatography. The quantification of bound residues in soil and in different fractions of soil humic substances has been performed using pyrolysis/scintillation-detected gas-chromatography. Microbial mineralization of the herbicide and soil organic matter has been also monitored. Retention of isoproturon residues after 30-days incubation ranged from 22% to 32% (non-extractable fraction). The radioactivity extracted in an aqueous environment was from 20% to 33% of the amount used for the treatment; meanwhile, methanol was able to extract another 48%. Both soils showed quantities of bound residues into the humin fraction higher than humic and fulvic acids. The total amount of residues retained into the organic matter of the soils was about 65 % of non-extractable fraction, and this percentage did not change with incubation time; on the contrary, the sorption rate of the retention reaction is mostly influenced by the clay fraction and organic content of the soil. Only a little part of the herbicide was mineralized during the experimental time.     

Extending large-scale forest inventories to assess urban forests

Urban areas are continuously expanding today, extending their influence on an increasingly large proportion of woods and trees located in or nearby urban and urbanizing areas, the so-called urban forests. Although these forests have the potential for significantly improving the quality the urban environment and the well-being of the urban population, data to quantify the extent and characteristics of urban forests are still lacking or fragmentary on a large scale. In this regard, an expansion of the domain of multipurpose forest inventories like National Forest Inventories (NFIs) towards urban forests would be required. To this end, it would be convenient to exploit the same sampling scheme applied in NFIs to assess the basic features of urban forests. This paper considers approximately unbiased estimators of abundance and coverage of urban forests, together with estimators of the corresponding variances, which can be achieved from the first phase of most large-scale forest inventories. A simulation study is carried out in order to check the performance of the considered estimators under various situations involving the spatial distribution of the urban forests over the study area. An application is worked out on the data from the Italian NFI.