The oxidation of di-(2-ethylhexyl) phthalate (DEHP) in solution using UV/H₂O₂ and direct UV photolysis are analyzed in this study. It was found that DEHP was 100% removal in the solution by 180-min UV/H₂O₂ treatment and 73.5% removal by 180-min direct UV photolysis. The effect of different factors, such as DEHP concentration, H₂O₂ concentration, and UV light intensity, on photochemical degradation was investigated. The degradation mechanism of DEHP and the acute toxicity of intermediates were also studied. The photochemical degradation process was found to follow pseudo-first-order kinetics. The results of our study suggested that the concentration with 40 mg/L H₂O₂ and 5 μg/mL DEHP in the solution at pH 7 with 10.0 × 10⁻⁶ Einstein l⁻¹ s⁻¹ UV was the optimal condition for the photochemical degradation of DEHP. The photochemical degradation with UV/H₂O₂ can be an efficient method to remove DEHP in wastewater.

Many natural vegetation species have been shown to be negatively affected by ozone. This study has investigated how the presence of competing species in a community affects two common responses to ozone: visible injury and senescence. Monocultures and mixtures of Trifolium repens and Lolium perenne were grown in large containers and were exposed in solardomes to either a rural episodic ozone profile (AOT40 of 12.86 ppm h) or control conditions (AOT40 of 0.02 ppm h) for 12 weeks. The proportion of ozone-injured or senesced leaves was different in the different regions of the canopy. The highest proportions of injured/senesced leaves were in the plant material growing at the edge of the canopy and the upper canopy, with a significantly lower proportion of injured leaves in the inner canopy. The presence of L. perenne increased the proportion of ozone-injured leaves in T. repens at the final harvest, whilst the presence of T. repens decreased the proportion of senesced leaves in L. perenne. In L. perenne, the proportion of injured leaves at the edge and inner canopy decreased significantly when grown in competition, whilst for T. repens the reverse effect occurred in the inner canopy only. Different mechanisms appeared to influence the interaction between response to ozone and competitors in these two species. In L. perenne the response to ozone may have been related to nitrogen supply, whereas in T. repens canopy structure was more important.

Atmospheric and sea sediment concentrations were measured for eight nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) and three unsubstituted PAHs in a suburban area and sea sediments in the Hiroshima Bay watershed area, Japan, from July to December, 2006 (atmospheric particulate matter) and in September and November, 2004 (sea sediments). Atmospheric concentration was higher in winter than summer for both nitro-PAHs and PAHs. Concentrations in sea sediments were less than 10%, and pattern was similar to those of atmospheric particles. Several combustion emission sources were also measured, and the 1-NP/Pyr ratio was compared to environmental values. The ratio of atmospheric and sea sediments were significantly lower than diesel particulate matters. Further, the vehicle emission loading and sea sedimentation loading was evaluated in this watershed area, and from the comparison, the existence of other important sources PAHs were suggested.

Metal dispersal in the Danube and Maritsa drainage basins resulting from metal mining activities in Bulgaria has been assessed through the collection of 611 samples of river water, river channel and floodplain sediment, and mine waste from over 218 sites. Concentrations of Cd, Cu, Pb, and Zn in river water were found to be highest in close proximity to locations of Cu and Pb-Zn mining regions in the Maritsa catchment. Downstream dispersal of solute metals in these catchments, and into the River Danube, was found to be limited by physical dilution and a well-buffered pH environment. Dispersal of contaminant metals in channel and floodplain sediment was found to be extensive. Contamination was particularly severe in the Rivers Timok and Iskar (Danube catchment) and the Topolnitsa, Chepelarska, and Arda Rivers (Maritsa catchment) and creates the potential of transboundary dispersal of contaminant metals.

Significant quantities of the broiler chicken (Gallus gallus domesticus) litter produced in the USA are being applied to pasture lands. The traditional surface- broadcast application of animal manure onto permanent pasture, however, may lead to high concentration of nutrients and pathogenic microorganisms near the soil surface that could be transported off site by runoff water. Subsurface banding of poultry litter has the potential to reduce nutrient and pathogen losses through runoff. However, this has not been thoroughly investigated. In this study, we used rainfall simulations to examine the effect of broiler litter application methods on the longevity of nutrient and Escherichia coli losses in runoff by successive runoff events. Runoff plots were constructed on Hartsells fine sandy loam (Typic Hapludults) soil with permanent Kentucky 31 tall fescue (Festuca arundinacea) pasture in Crossville, AL. Treatments included two methods of litter application (surface broadcast and subsurface banding), commercial fertilizer, and control (no litter or fertilizer applied). To evaluate the longevity of nutrient losses, simulated rainfall (110 mm h⁻¹) was applied to each plot on days 1, 7, and 14 following litter and fertilizer applications. Total P (TP), inorganic N, and E. coli concentrations were all significantly greater in runoff from broadcast litter application than the subsurface litter banding treatments. The TP losses from broadcast litter applications averaged 6.5 times those from subsurface litter applications. About 81% of the runoff TP concentration was in the form of dissolved reactive phosphorus for both litter application methods. The average losses of NO₃-N and total suspended solids from subsurface litter banding plots were 358 g ha⁻¹ and 68 kg ha⁻¹ compared to 462 and 60 kg ha⁻¹ for the broadcast method, respectively. This study shows that subsurface banding of broiler litter into perennial grassland can substantially reduce nutrient and pathogen losses in runoff compared to the traditional surface-broadcast practice.

After elevated concentrations of perfluorooctanoate (PFO) were found in river and groundwater in the vicinity of a fluoropolymer manufacturing facility, numerous soils at adjacent sites were sampled in 2007. Within a 5-km northeast-oriented sector around a probable point source, 20 forest sites were investigated and compared to deposition and groundwater data. PFO concentrations up to 600 µg/kg were detected in the soils, and PFO concentrations typically decreased toward deeper soil depths. In mixed or deciduous forests, maximum concentrations of PFO occurred in the topsoil, pointing to the favorable decomposition and incorporation of deciduous litter. PFO concentrations of the organic layer over the 20 sampling sites were interpolated using ordinary kriging. Highest PFO content in the organic layer was located about 500 m away from the point source in the regional wind direction, decreasing asymptotically outwards. Long-term monitoring data pointed to an accumulation of PFO over time in the organic layer. The data suggest that PFO might be released in the course of litter decomposition and transported toward deeper soil regions only gradually. The soils' PFO concentrations reflect the deposition data. The transport link toward groundwater is currently established in lysimeter studies.

Background, aim, and scope Diffusive gradients in thin films (DGT) have been recognized as a suitable tool to assess in situ metal bioavailability in soils. Mine tailings have some singular characteristics such as high heavy-metal concentrations, low pH, or absence of water retention capacity that may compromise the correct application of this technique whose applicability is known to be pH dependent. The goal of this study was to determine the response of DGT devices in heavy-metal-polluted mine tailings with different pH. In addition some experiments were performed in order to determine the effect of acidic pH and dissolved ions on the binding properties of the chelating resin. Materials and methods We tested DGT devices on three different mine tailings: acid pH 3, acid tailing limed to pH 5.5, and neutral pH 7.2. The tailings showed high metal concentrations, e.g., 7,000 mg kg⁻¹ Pb, 9,000 mg kg⁻¹ Zn, and 380 mg kg⁻¹ Cu. Diffusive and Chelex resin gels were prepared according to previously published methods. Two chelating resins and diffusive gels thicknesses (0.4 and 0.7 mm) were tested. Four DGT devices of each type were placed during 24 h in pots (one device per pot) containing 1 kg mine tailings in a climate chamber with humidity (50-90%) and controlled temperature conditions (night 16°C and day 23°C). Pots were irrigated with deionized water to field capacity, and then two different experiments were performed: (a) allowing free drainage and (b) maintaining the water saturation. In addition, we tested DGT devices in solutions at pH 3 with similar properties to the soil solution measured in the acid tailing. Eluted Zn, Cd, Pb, and Cu from the chelating resins were measured using inductively coupled plasma-optical emission spectrometer (ICP-OES; Vista-MPX Varian). Results and discussion The metal concentrations taken up by the DGT devices were affected by the different pH values of the tailings. The highest metal concentrations measured with DGT (C DGT) were obtained in the pH 3 treatments (both saturated and free drainage). Significant differences for C DGT were observed between water-saturated and free drainage treatments in the acid pH 3 tailing. When limed pH 5.5 tailing and neutral pH 7 tailing were considered, these differences were lower and not significant. In pH 3 tailings low values for C DGT/C soil solution were obtained (<0.06), indicating that these soils have a low capacity to resupply depleted metals to the solution. The limed acid tailing and the neutral tailing showed values between 0.05 and 0.94 indicating a much more rapid resupply from the solid phase. Deployment under water-saturated conditions yielded much higher C DGT values than under free drainage, indicating the importance to adequately control the moisture content in these soils with poor water retention capacity. In solutions with pH 3 mimicking the soil solution composition of the tailings, a loss of the binding capacity of the resin of 50-60% and 60-80% for Zn in 0.7-mm DGT and 0.4-mm DGT devices, respectively, was observed. As a consequence, 0.7-mm DGT devices had better reliability to carry out in situ determinations in solutions with high metal concentrations and low pH. Conclusions The use of DGT in mining soils can be a promising tool to study bioavailable metals concentrations in mine tailings but it has to be used carefully under acidic pH. Competition with other cations that are present at very high concentrations may hinder the accumulation of metals by the chelating resins, which should be tested under the conditions of the particular mine tailing.

The residual brine of the Cerro Prieto Geothermal Field (CPGF) is disposed in an evaporation pond. The seepage of this pond has contaminated the water and agricultural soil around it. The contamination of the groundwater towards the southwest by the evaporation pond, in the direction of the regional flow, has been shown before. Hydrogeochemical modeling (PHREEQCI) and Schoeller and Piper diagrams have been used in this work to show that the chemical composition of the groundwater in villages neighboring CPGF is the product of mixing between irrigation water from the Colorado River and brine from the evaporation pond. The high potassium concentration in the water and the relative increase in concentration of sodium and chlorides along the flow path as well as the hydrogeochemical models for this system explain this mixing process. This work will allow proposing new managing techniques to avoid the presence of the residual brine in the groundwater of agricultural lands.

The degradation of diethyl phthalate (DEP) in aqueous solution by titanium dioxide (TiO2) photocatalysis has been investigated in our research. DEP was completely removed in the solution by 50-min irradiation. Results show that DEP degradation rate was affected by initial DEP concentration, photocatalyst amount, light intensity, and pH. Photocatalytic degradation intermediates were identified by gas chromatography-mass spectrometry intermediates were identified by gas chromatography-mass spectrometry. The major intermediates are methyl benzoate, ethyl benzoate, and carboxylic derivatives. The photocatalytic degradation process was found to obey first-order reaction. Consequently, the result of photocatalytic degradation could be an efficient method of DEP removal from wastewater.

Polycyclic aromatic hydrocarbons (PAHs); their derivatives nitro, and methyl-PAHs; n-alkanes; and organic acids were investigated in the aerosol samples collected during two field campaigns conducted at three sampling stations in an industrialized city in southern Italy. The main sources affecting the atmosphere and its toxicity were investigated by means of the diagnostic ratios of: specific particulate-phase PAHs, marker compounds among nitro-PAHs, alkanes, and acids, the dominant wind direction, daily and seasonal abundance of carcinogenic organic substances. The potential importance of the non-regulated pollutants to assess the air quality was confirmed; in fact the carcinogenic organic compounds showed to have scarce correlation with particulate matter (PM) concentration. An exceptionally high variability of toxic compounds at a daily scale was due to meteorological condition causing periods of extremely high pollution levels.