Stormwater is a potential and readily available alternative source for potable water in urban areas. However, its direct use is severely constrained by the presence of toxic pollutants, such as heavy metals (HMs). The presence of HMs in stormwater is of concern because of their chronic toxicity and persistent nature. In addition to human health impacts, metals can contribute to adverse ecosystem health impact on receiving waters. Therefore, the ability to predict the levels of HMs in stormwater is crucial for monitoring stormwater quality and for the design of effective treatment systems. Unfortunately, the current laboratory methods for determining HM concentrations are resource intensive and time consuming. In this paper, applications of multivariate data analysis techniques are presented to identify potential surrogate parameters which can be used to determine HM concentrations in stormwater. Accordingly, partial least squares was applied to identify a suite of physicochemical parameters which can serve as indicators of HMs. Datasets having varied characteristics, such as land use and particle size distribution of solids, were analyzed to validate the efficacy of the influencing parameters. Iron, manganese, total organic carbon, and inorganic carbon were identified as the predominant parameters that correlate with the HM concentrations. The practical extension of the study outcomes to urban stormwater management is also discussed.

Removal of petroleum hydrocarbon (PHC) contamination that is hazardous and often prevalent in soils would benefit from a rapid detection technique. Visible and near-infrared spectroscopy (VIS-NIRS) has a large potential as a rapid detection technique for PHC in soils. Nevertheless, the combined influence of oil concentration, moisture content and clay content on soil reflectance spectra and the accuracy of the technique have yet received little attention. The objective of this study was to investigate the combined influence of oil concentration and moisture and clay contents on the spectral characteristics of diesel-contaminated soils and the quality of calibration models developed for polycyclic aromatic hydrocarbons (PAH) in soils using VIS-NIRS. With partial least-squares regression data from a systematic experimental design using 150 artificially contaminated soil samples, results showed that soil diffuse reflectance decreased with increasing oil concentration, clay and moisture contents. The trend was less defined in relation to moisture and clay due mainly to the interaction effects of the soil matrices as mediated by the oil. The PAH partial least squares cross-validation showed best performance with the lowest oil concentration and clay content at 20 % moisture with r ² of 0.89, root mean square error of prediction of 0.201 mg/kg and ratio of the standard error of prediction to the standard deviation of the reference data in the validation set of 2.75. Analysis of variance showed that the interaction effects of oil concentration, moisture and/or clay content significantly (p < 0.05) affected the quality of the PAH models.

Buenos Aires Province (República Argentina) has undergone, in the last years, a great increase in agricultural activities based on the incorporation of new technologies and reduction of diversity to meet the increasing food demand. The increase of intensive agricultural systems in Argentina involves the use of fertilizers and pesticides such as herbicides, insecticides, and fungicides. Chlorpyrifos is one of the insecticides most widely used in these crops and constitutes a risk for human health, birds, and aquatic biota such as macroinvertebrates and fishes. In order to assess the possible contamination that the use of this product may represent for the environment, it is necessary to study its interaction with the different types of soils because fate and transport of environmental pollutants may be influenced by their interactions with soil particles. The behavior of chlorpyrifos was analyzed through the study of the recoveries from spiked solid environmental matrices. A strong dependence with organic matter content was observed along with an important dependence with the initial concentrations employed. Here, we show that chlorpyrifos behavior on solid matrices not only depends on soil chemical composition. A significant dependence of recovery percentages with initial concentrations of the pesticide was evident in all cases. Recovery percentages decreased with an increase of the initial concentration employed, no matter the variations in matrices of chemical compositions.

In this work, a coal combustion ash (CCA) has been tested as an alternative low-cost sorbent to commercial activated carbons (GAC) for cadmium and zinc removal from polluted water. To this aim, the effect of pH and metal concentration on CCA adsorption capacity has been investigated, and a comparative analysis with GAC has been carried out in the same experimental conditions. Furthermore, in order to improve CCA adsorption capacity, two different activation treatments of raw CCA have been tested. In particular, the CCA was subjected to a gasification process conducted with steam and to different acidic treatments, conducted either with hydrochloric acid or nitric acid at different acid concentrations. Experimental results showed that all the acid treatments determined a substantial reduction of both cadmium and zinc adsorption capacity. Differently, the steam gasification determined a substantial increase in adsorption capacity with respect to raw CCA, in particular for zinc as its adsorption capacity resulted even higher than the correspondent of GAC. Finally, a thorough analysis of sorbent physical and chemical properties and of adsorption data allowed the individuation of the main cadmium/zinc adsorption mechanism both on CCA and activated carbon, adequately described by the Freundlich model.

N-Nitrosodimethylamine (NDMA) is recently defined as one of nitrogenous disinfection by-products with high carcinogenicity and can be frequently detected in finished water. The decomposition of NDMA in water using nanoscale zero-valent iron (NZVI) in the presence of aluminum and iron salts was investigated in this paper. The results showed that some salts can enhance the removal of NDMA by commercial NZVI in the order of Al(SO) >> AlCl > FeSO > NaSO ≈ NZVI alone, and the highest NDMA removal was 87.3 % in the presence of Al(SO). NDMA removal varied with the addition of Al(SO), NZVI dosage, initial NDMA concentration, solution pH, and temperature. The reduction of NDMA increased with the dosage of Al(SO) and NZVI, which follows a pseudo-first-order kinetics model. The removal of NDMA by NZVI was higher in acidic pHs than in alkaline ones, and the highest removal was found at pH 5. Higher reaction temperature can improve the removal of NDMA and reduce the reaction time. Based on the total nitrogen balance, most nitrogen of NDMA was converted to ammonium and dimethylamine.

In this study, chemical oxidation was applied to treat three contaminated sediments. All the sediments were contaminated with mineral oil, polycyclic aromatic hydrocarbons and heavy metals and had an organic matter content ranging from 2.4 to 7.6 %. The natural oxidant demand of the sediments was determined during treatment with two different types of oxidants (potassium permanganate and sodium persulfate), and the effect of these oxidants on the heavy metal release and on the microbial community was investigated. The natural oxidant demands of the sediments under persulfate treatment were lower (30–100 g kg⁻¹) than the ones treated with permanganate (50–450 g kg⁻¹). Cr was released during the application of permanganate whereas Zn and Pb were released under persulfate treatment. qPCR results showed that permanganate and persulfate, both at a concentration of 150 g kg⁻¹, caused a decrease (2 log units) in the number of 16S rRNA gene of total bacteria in the sediment having the lowest organic matter content. However, the total ATP, considered as a biomarker for microbial activity, was below detection limit in all sediments in the presence of at least 150 g kg⁻¹ oxidant. Only permanganate induced a shift in the structure of the microbial community.

Four species of trees were selected to evaluate the tolerance to heavy crude oil contamination by means of a tolerance index integrating germination, height, biomass and survival as variables. Fresh seeds to Cedrela odorata (tropical cedar), Haematoxylum campechianum (tinto bush), Swietenia macrophylla (mahogany) and Tabebuia rosea (macuilis) were planted in a Vertisol to which heavy crude petroleum was added at four different treatments (C0, 0; C1, 18,940; C2, 44,000; and C3, 57,000 mg kg⁻¹), with the control being uncontaminated soil. The experiment was carried out in a greenhouse during 203 days with a completely random design. The presence of petroleum in soil stimulated and increased germination of S. macrophylla and C. odorata, accelerated the germination of T. rosea and did not affect the germination of H. campechianum. The height and biomass of all species was reduced in the presence of petroleum in the soil. The survival of S. macrophylla and H. campechianum was not affected by petroleum at any concentration studied. On the other hand, C. odorata and T. rosea showed high mortality at all concentrations. The tolerance index showed that S. macrophylla was best at tolerating petroleum in soil and could be employed as a productive alternative for the advantageous use of contaminated sites. The use of tree species could be important because of the great potential of trees for phytoremediation due to their long life, biomass and deep roots that can penetrate and remediate deeper soil layers.

Robust and cheap, biofiltration is one of the most used methods for the biological treatment of industrial gaseous odours and VOCs emissions. The chemical, physical and microbial properties, as well as the economical impact of 11 organic and inorganic packing materials potentially suitable for biofiltration, have been investigated in order to select the most relevant for the treatment of rendering gaseous emissions. Fibrous materials such as peat and coconut fibres are predisposed to compaction. Moreover, according to their low expected running period, their implementation remains expensive, such as activated carbon which induce overweening costs (>100,000€ an -1 for the treatment of 40,000 m3 h-1 with a 60-s empty bed gas residence time). Considering economical aspects, physico-chemical and biological properties, pines barks, composted wood mulch and expanded schist seem fit for this application. The performance of these materials was therefore investigated in a pilot-scale study conducted on a rendering site. According to its appropriate pH (8.62) and water-holding capacity (1.41 g g-1) and its highest nutrients content and colonization at the biofilter start-up (93 g of ATP m-3, 29.10 13 CFU m-3), composted would mulch show the best odour removal efficiency during the 134 days of operation. Performances ranged between 75 and 93 % for the treatment of odourous inlet load between 1.16 and 10.10·106 ouE m-3 h-1 with an empty bed gas residence time of 47 s. However, the pressure drop of the compost bed decreased, suggesting structural changes which may impact the performances in the long term. © 2013 Springer Science+Business Media Dordrecht.

The use of Cu-based fungicide can pose a risk to nearby surface water bodies due to the run-off of accumulated Cu from agricultural soils. In 2008, we conducted a reconnaissance survey of the presence and concentration of copper in sediments at 18 sites within the Yarra River Catchment, an important horticultural production system in south-eastern Australia. Observed Cu concentrations in sediment samples from the study sites (mean (95 % confidence interval) 12.0 (10.6-13.6) mg/kg dry weight) were similar to the concentrations present in the samples from the reference sites (mean (95 % confidence interval) 12.0 (6.7-16.8) mg/kg dry weight). The data on Cu and other metals in the sediments suggest that that there is unlikely to have been wide spread, diffuse, off-site transport of Cu from the soils of horticultural properties to nearby surface waterways in the Yarra River Catchment and that that observed sediment metal concentrations are unlikely to pose an ecological risk to sediment-dwelling organisms at the study sites. © 2013 Springer Science+Business Media Dordrecht.

The effects of six phosphate (P) fertilizers in mobilizing and immobilizing water-soluble lead (Pb) were determined in a contaminated soil (Alfisol from Shaoxing) from China and four Australian soils (an Oxisol from Twonsville Queensland and three South Australian soils from Cooke Plains (Typic Palexeralf)), Inman Valley (Vertisol), and Two Wells (Natric Palexeralf). The fertilizers tested were single superphosphate (SSP), triple superphosphate (TSP), monoammonium phosphate (MAP), diammonium phosphate (DAP), monocalcium phosphate (MCP), and dicalcium phosphate (DCP) to produce an initial P concentration of 1,000 mg/L. The Chinese soil contained 16,397 mg/kg total Pb, but the Australian soils were uncontaminated. The four Australian soils were each spiked with 1,000 mg Pb/kg soil (as Pb(NO3)2) and incubated for a month. Single superphosphate treatments decreased total soluble Pb in soil solution to 2-14 % of those of the nil-P (0P) treatment in the four Pb-spiked soils and to 48 % in the Chinese Pb-contaminated soil. The DAP treatment followed by the MAP treatment greatly increased the total soluble Pb in soil solution up to 135-500 % of the 0P treatment, except in the Two Wells soil. MCP could decrease the total soluble Pb in Cooke Plains, Inman Valley, Shaoxing, and Two Wells soils while increase it in the Queensland soil; DCP decreased the total soluble Pb in Cooke Plains and Queensland soils while increased it in the Shaoxing and Inman Valley soils. There were close relationships between the total soluble Pb, total soluble Al, and total soluble Fe in the water extracts of each. Soluble Al and Fe ions in soil solution increased soluble Pb concentrations. We conclude that not all phosphate fertilizers immobilize Pb in soils equally well. SSP and TSP are excellent Pb-immobilizing fertilizers, while MAP and DAP are strong Pb-mobilizing fertilizers. MCP and DCP are either Pb-immobilizing fertilizers or Pb-mobilizing fertilizers depending on their reactions with individual soils. © 2013 Springer Science+Business Media Dordrecht.