Characterization and classification of complex PAH samples using GC-qMS and GC-TOFMS

The aim of this study was to compare the polycyclic aromatic hydrocarbon (PAH) contents in a number of complex samples, including soil samples from industrial sites, anti-skid sand, urban dust and ash samples from municipal solid waste incinerators. The samples were characterized by routine analysis of PAHs (gas chromatography–quadrupole mass spectrometry) and gas chromatography–time of flight mass spectrometry (GC–TOFMS). Classification of the samples by principal component analysis (PCA) according to their composition of PAHs revealed that samples associated with traffic and the municipal incinerator formed homogeneous clusters, while the PAH-contaminated soils clustered in separate groups. Using spectral data to resolve co-eluting chromatographic peaks, 962 peaks could be identified in the GC–TOFMS analysis of a pooled sample and 123–527 peaks in the individual samples. Many of the studied extracts included a unique set of chemicals, indicating that they had a much more diverse contamination profile than their PAH contents suggested. Compared to routine analysis, GC–TOFMS provided more detailed information about each sample and in this study a large number of alkylated PAHs were found to be associated with the corresponding unsubstituted PAHs. The possibility to filter peaks according to different criteria (e.g. to include only peaks that were detected in the analysis of another sample) was explored and used to identify unique as well as common compounds within samples. This procedure could prove to be valuable for obtaining relevant chemical data for use in conjunction with results from various biological test systems.     

Determination of trichloroacetic acid in environmental studies using carbon 14 and chlorine 36

Radioisotopes carbon 14 and chlorine 36 were used to elucidate the environmental role of trichloroacetic acid (TCA) formerly taken to be a herbicide and a secondary air pollutant with phytotoxic effects. However, use of ¹⁴C-labeling posed again known analytical problems, especially in TCA extraction from the sample matrix. Therefore—after evaluation of available methods—a new procedure using decarboxylation of [1,2-¹⁴C]TCA combined with extraction of the resultant ¹⁴C-chloroform with a non-polar solvent and its subsequent radiometric measurement was developed. The method solves previous difficulties and permits an easy determination of amounts between 0.4 and 20 kBq (10–500 ng g⁻¹) of carrier-less [1,2-¹⁴C]TCA in samples from environmental investigations. The procedure is, however, not suitable for direct [³⁶Cl]TCA determination in chlorination studies with ³⁶Cl. Because TCA might be microbially degraded in soil during extraction and sample storage and its extraction from soil or needles is never complete, the decarboxylation method—i.e. 2 h TCA decomposition to chloroform and CO₂ in aqueous solution or suspension in closed vial at 90 °C and pH 4.6 with subsequent CHCl₃ extraction—is recommended here, estimated V < 7%. Moreover, the influence of pH and temperature on the decarboxylation of TCA in aqueous solution was studied in a broad range and its environmental relevance is shown in the case of TCA decarboxylation in spruce needles which takes place also at ambient temperatures and might amount more than 10–20% after a growing season. A study of TCA distribution in spruce needles after below-ground uptake shows the highest uptake rate into current needles which have, however, a lower TCA content than older needle-year classes, TCA biodegradation in forest soil leads predominatingly to CO₂.     

Spatial variability of arsenic and chromium in the soil water at a former wood preserving site

Contamination of industrial sites by wood preservatives such as chromated copper arsenate (CCA) may pose a serious threat to groundwater quality. The objective of this study was to characterise the spatial variability of As and Cr concentrations in the solid phase and in the soil water at a former wood impregnation plant and to reveal the fundamental transport processes. The soil was sampled down to a depth of 2m. The soil water was extracted in situ from the vadose zone over a period of 10 months at depths of 1 and 1.5m, using large horizontally installed suction tubes. Groundwater was sampled from a depth of 4.5m. Results showed that arsenic and chromium had accumulated in the upper region of the profile and exhibited a high spatial variability (As: 21-621 mg kg(-1); Cr: 74-2872 mg kg(-1)). Concentrations in the soil water were high (mean As 167 microg L(-1); Cr: 62 microg L(-1)) and also showed a distinct spatial variability, covering concentration ranges up to three orders of magnitude. The variability was caused by the severe water-repellency of the surface soil, induced by the concurrent application of creosote wood preservatives, which leads to strong preferential flow as evident from a dye experiment. In contrast to soil water concentrations, only low As concentrations (<12 microg L(-1)) were detected in the groundwater. High Cr concentrations in the groundwater (approx. 300 microg L(-1)), however, illustrated the pronounced mobility of chromium. Our study shows that at sites with a heterogeneous flow system in the vadose zone a disparity between flux-averaged and volume-averaged concentrations may occur, and sampling of soil water might not be adequate for assessing groundwater concentrations. In these cases long-term monitoring of the groundwater appears to be the best strategy for a groundwater risk assessment.     

Metals distribution in soils around the cement factory in southern Jordan

Thirty one soil samples were collected from south Jordan around the cement factory in Qadissiya area. The samples were obtained at two depths, 0-10 cm and 10-20 cm and were analyzed by atomic absorption spectrophotometery for Pb, Zn, Cd, Fe, Cu and Cr. Physicochemical factors believed to affect their mobility of metals in soil of the study area were examined such as; pH, TOM, CaCO3, CEC and conductivity. The relatively high concentrations of lead, zinc and cadmium in the soil samples of the investigated area were related to anthropogenic sources such as cement industry, agriculture activities and traffic emissions. It was found that the lead, zinc and cadmium have the highest level in area close to the cement factory, while the concentration of chromium was low. This study indicate that all of the metals are concentrated on the surface soil, and decreased in the lower part of the soil, this due to reflects their mobility and physical properties of soil and its alkaline pH values. The use of factor analysis showed that anthropogenic activities seem to be the responsible source of pollution for metals in urban soils.     

Depth profiles of radiocarbon and carbon isotopic compositions of organic matter and CO2 in a forest soil

Depth profiles of the specific activities of (14)C and carbon isotopic compositions (Delta(14)C, delta(13)C) in soil organic matter and soil CO(2) in a Japanese larch forest were determined. For investigating the transport of CO(2) in soil, specific activities of (14)C, Delta(14)C and delta(13)C in the organic layer, and atmospheric CO(2) in the same forest area were also determined. The specific activity of (14)C and Delta(14)C in the soil organic matter decreased with the increase in depth of 0-60cm, while that of soil CO(2) did not vary greatly at a soil depth of 13-73cm and was more prevalent than that of atmospheric CO(2). Peaks of specific activities of (14)C appeared at the depth of 0-4cm and Delta(14)C values were positive in the depth range from 0 to 15cm. These results suggest that the present soil at a depth of 0-4cm had been produced from the mid-1950s up until 1963, and the bomb C had reached the depth of 15cm in the objective soil area. The delta(13)C in the soil organic matter increased at the depth of 0-55cm, while that of soil CO(2) collected on 8 November 2004 decreased rapidly at the depth of 0-13cm and only slightly at the depth of 53-73cm. By combining the Delta(14)C and delta(13)C of the respective components and using the Keeling plot approach it was made clear that the entering of atmospheric CO(2) showed a large contribution to soil CO(2) at the depth of 0-13cm and a negligible contribution at the depth of 53-73cm for soil air collected on 8 November 2004. Respiration of live roots was presumed to be the main source of soil CO(2) at the depth of 53-73cm on 8 November 2004.     

The effect of model structure and data in modeling land conditions in disturbed complex ecosystems

Off-road vehicles increase soil erosion by reducing vegetation cover and other types of ground cover, and by changing the structure of soil. The investigation of the relationship between disturbance from off-road vehicles and the intensity of the activities that involve use of vehicles is essential for water and soil conservation and facility management. Models have been developed in a previous study to predict disturbance caused by off-road vehicles. However, the effect of data on model quality and model performance, and the appropriate structure of models have not been previously investigated. In order to improve the quality and performance of disturbance models, this study was designed to investigate the effects of model structure and data. The experiment considered and tested: (1) two measures of disturbance based on the Vegetation Cover Factor (C Factor) of the Revised Universal Soil Loss Equation (RUSLE) and Disturbance Intensity; (2) model structure using two modeling approaches; and (3) three subsets of data. The adjusted R-square and residuals from validation data are used to represent model quality and performance, respectively. Analysis of variance (ANOVA) is used to identify factors which have significant effects on model quality and performance. The results of the ANOVA show that subsets of data have significant effects on both model quality and performance for both measures of disturbance. The ANOVA also detected that the C Factor models have higher quality and performance than the Disturbance models. Although modeling approaches are not a significant factor based on the ANOVA tests, models containing interaction terms can increase the adjusted R-squares for nearly all tested conditions and the maximum improvement can reach 31%.     

Environmentally adjusted productivity measurement: an Australian case study

This paper critically examines various methods for estimating productivity incorporating environmental effects for the Australian agricultural sector. The agricultural sector has been selected because of its strategic position in the economy of Australia. The findings of this study indicate that the application of environmentally adjusted productivity methods is a credible approach to measure productivity, in the context of sustainable development. Although the empirical findings of this research are case study specific, the results provide evidence supporting the adoption of these techniques to other sectors of the economy when measuring productivity and needing to be cognisant of sustainable development. The findings suggest that adjusting for the environmental impacts of soil erosion can result in higher or lower agricultural productivity depending on the assumptions we make regarding damage costs of erosion. It is argued in this paper that, for soil erosion in Australia, assumptions yielding higher productivity (i.e., upwardly adjusted) are justified. Finally, the findings of this study and the use of the methods presented point to important gaps in data availability. This gap needs to be addressed by policy makers if sustainable development objectives are to be credibly assessed using these techniques.     

Socioeconomic benefits of conserving Iran’s water resources through modifying agricultural practices and water management strategies

Sustainable development requires modifying the current consumption pattern of natural resources. This study investigates efficient tactics for reducing the unsustainability and inefficiency of human’s food-related blue water consumption alongside improving national environmental and socioeconomic status. As a case study for Iran, 15 alternative management scenarios (AMS) were defined compared to the current on-farm management, and their effects were assessed on a monthly scale. Based on the results, 45.5 billion m³ y⁻¹ (BCM) blue water is consumed within the croplands, 78% and 34% of which are unsustainable and inefficient, respectively. AMCs reduces the unsustainable and inefficient blue water consumption by 2–17 BCM and 2–13 BCM, respectively. The combination of yield gap closure, drip irrigation, soil mulching, and deficit irrigation has the largest effect on blue water saving; it releases or changes the status of monthly blue water scarcity in 11 provinces; increases field-employees by 132%, food security by 9%, international food-export by 87%, and gross domestic production by 54%. However, it doesn’t fully address blue water overconsumption in the summer period; hence, further measures are needed to reduce blue water scarcity to the sustainable level in these environmental hotspots.     

Soil compaction--indicators for the assessment of harmful changes to the soil in the context of the German Federal Soil Protection Act

Soil compaction in agriculture induced by large-scale equipment is of growing concern. Heavy wheel loads used in arable cropping have the potential to cause irreversible damage to the subsoil structure and may lead to harmful soil compaction. In order to sustain or improve soil health or fitness on a sustainable basis, indicators are needed to assess the changes in the soil structure and the respective soil functions. This requires an adequate verification of methods for distinguishing between the impairment of soil structure and the disruption of soil functions, and for the respective subject of protection. In this article the link between existing models of soil physical prognosis, practical guidelines, and criteria for the identification of affected soil structure is demonstrated, and a viable concept to distinguish harmful changes to the soil is presented. The concept consists of methods for soil physical analysis such as "pre-compression stress" and "loading ratio", practical recommendations for best management practice, and an indicator-based model for the identification of harmful subsoil compaction derived from a research project for the German Federal Environmental Agency, making it possible to determine for a respective location the required level of action far beyond the common practice of precautions against harmful soil compaction.     

土壤对石化工业废水的吸咐试验分析

通过土壤对石化工业废水的吸附试验分析，可以预测工程废水对地下水的影响情况，对保护当地地下水水质，指导工程环境建设具有十分积极的作用