Isosteric heats (ΔH) of sorption/desorption of phenanthrene were determined for carbonaceous materials (Pahokee peat, lignite, and high-volatile bituminous coal) and two soils based on reported equilibrium sorption/desorption isotherms at four different temperatures (4, 20, 46 and 77 °C). In addition, ΔH for desorption of native phenanthrene was determined to elucidate the “aging” effect by equilibrating samples with water at six temperatures (20, 40, 53, 61, 73, and 86 °C). Isosteric heats decreased with increasing solute concentration and were in a range of 19–35 kJ mol−1. Values higher than the heat of octanol–water phase transfer for phenanthrene (19 kJ mol−1) imply that both partitioning and adsorption processes are involved for these materials, where the sorptive contributions from both processes were estimated based on the phenanthrene thermodynamic data. Moreover, on the basis of ΔH values of desorption, release of native and spiked phenanthrene from our samples was similar.

Tropospheric ozone is a secondary pollutant whose primary sources are volatile organic compounds and nitrogen oxides. The national standard is exceeded on a third of summer days in some areas of the Chilean Metropolitan Region (MR). This study reports normalized springtime experimental emissions factors (EF) for biogenic volatile organic compounds from tree species corresponding to approximately 31% of urban trees in the MR. A Photochemical Ozone Creation Index (POCI) was calculated using Photochemical Ozone Creation Potential of quantified terpenes. Ten species, natives and exotics, were analysed using static enclosure technique. Terpene quantification was performed using GC-FID, thermal desorption, cryogenic concentration and automatic injection. Observed EF and POCI values for terpenes from exotic species were 78 times greater than native values; within the same family, exotic EF and POCI values were 28 and 26 times greater than natives. These results support reforestation with native species for improved urban pollution management.

This study investigated the simultaneous desorption of trace metal elements and polychlorinated biphenyl (PCB) from mixed contaminated soil with a novel combination of biosurfactant saponin and biodegradable chelant S,S-ethylenediaminedisuccinic acid (EDDS). Results showed significant promotion and synergy on Pb, Cu and PCB desorption with the mixed solution of saponin and EDDS. The maximal desorption of Pb, Cu and PCB were achieved 99.8%, 85.7% and 45.7%, respectively, by addition of 10 mM EDDS and 3000 mg L−1 saponin. The marked interaction between EDDS and saponin contributed to the synergy performance. The sorption of EDDS and saponin on soil was inhibited by each other. EDDS could enhance the complexation of metals with the saponin micelles and the solubilization capabilities of saponin micelles for PCB. Our study suggests the combination of saponin and EDDS would be a promising alternative for remediation of co-contaminated soils caused by hydrophobic organic compounds (HOCs) and metals.

Bioaccessibility tests can be used to improve contaminated land risk assessments. For organic pollutants a ‘sink’ is required within these tests to better mimic their desorption under the physiological conditions prevailing in the intestinal tract, where a steep diffusion gradient for the removal of organic pollutants from the soil matrix would exist. This is currently ignored in most PBET systems. By combining the CEPBET bioaccessibility test with an infinite sink, the removal of PAH from spiked solutions was monitored. Less than 10% of spiked PAH remained in the stomach media after 1 h, 10% by 4 h in the small intestine compartment and c.15% after 16 h in the colon. The addition of the infinite sink increased bioaccessibility estimates for field soils by a factor of 1.2–2.8, confirming its importance for robust PBET tests. TOC or BC were not the only factors controlling desorption of the PAH from the soils.

Experiments were conducted to analyze processes impacting arsenic transport in irrigation water flowing over bare rice-field soils in Bangladesh. Dissolved concentrations of As, Fe, P, and Si varied over space and time, according to whether irrigation water was flowing or static. Initially, under flowing conditions, arsenic concentrations in irrigation water were below well-water levels and showed little spatial variability across fields. As flowing-water levels rose, arsenic concentrations were elevated at field inlets and decreased with distance across fields, but under subsequent static conditions, concentrations dropped and were less variable. Laboratory experiments revealed that over half of the initial well-water arsenic was removed from solution by oxidative interaction with other water-column components. Introduction of small quantities of soil further decreased arsenic concentrations in solution. At higher soil-solution ratios, however, soil contributed arsenic to solution via abiotic and biotic desorption. Collectively, these results suggest careful design is required for land-based arsenic-removal schemes.

Methods for determining bioavailability of organic contaminants suffer various operational limitations. We explored the use of stable isotope labeled references in developing an isotope dilution method (IDM) to measure the exchangeable pool (E) of pyrene and bifenthrin as an approximation of their bioavailability in sediments. The exchange of deuterated bifenthrin or pyrene with its native counterpart was completed within 48 h. The derived E was 38–82% for pyrene and 28–59% for bifenthrin. Regression between E and the sum of rapid and slow desorption fractions obtained from sequential desorption showed a slope close to 1.0. The ability of IDM to predict bioavailability was further shown from a strong relationship (r2 > 0.93) between E and bioaccumulation into Chironomus tentans. Given the abundance of stable isotope labeled references and their relatively easy analysis, the IDM has the potential to become a readily adoptable tool for estimating organic contaminants bioaccessibility in various matrices.

Particulate matter (PM) in Masterton, New Zealand, a rural community with a population of 20 000, was studied during the winter to gain an understanding of the carbonaceous species and their influence on PM concentrations. The average PM10 concentration during the winter was 21.0±14.8 µg m–3, of which 64% was PM2.5. PM2.5 concentrations were found to be the main cause of elevated PM10 concentrations, and were responsible for exceedances of the New Zealand National Environmental Standard for PM10. Carbonaceous species were 47 and 77% of the total PM10 and PM2.5, respectively. Organic carbon (OC) concentrations were always higher than elemental carbon (EC) concentrations. OC and EC concentrations showed excellent correlation with PM2.5 concentrations, suggesting that combustion processes were the dominant source of PM. Stable isotope analysis yielded δ13C values ranging from –24.9 to –27.6‰, which is indicative of wood combustion. Analysis of particle–phase PAHs by thermal desorption GC/MS yielded an average total PAH concentration of 38.9±25.9ng m–3, accounting for 0.3% of the PM2.5. Analysis of all of the results revealed that residential wood burning for domestic heating was the main source of PM pollution in Masterton. The results of this study suggest that a PM10 standard alone, particularly in areas where wood combustion is common, may not be providing an adequate level of protection for the exposed population.

This study investigated the desorption behavior of polychlorinated biphenyls (PCBs) from marine plastic pellets. Long-term desorption experiments were conducted using field-collected polyethylene (PE) pellets. The results indicate that the desorption kinetics highly depends on the PE-water partition coefficients of PCB congeners. After 128d of the experiment, the smallest congener considered (CB 8) had desorbed nearly completely (98%), whereas major fractions (90–99%) of highly chlorinated congeners remained in the pellets. An intraparticle diffusion model mostly failed to reproduce the desorption kinetics, whereas an aqueous boundary layer (ABL) diffusion model well approximated the data. The desorption half-lives are estimated to 14d to 210years for CB 8 to CB 209 in an actively stirred solution (ABL thickness: 30μm). Addition of methanol to water enhanced the desorption to a large extent. A need for further work to explore roles of organic matter in facilitating solute transfer is suggested.

We investigated the influence of salinity on sediment inorganic nitrogen dynamics in three Portuguese estuaries (Cávado, Ave and Douro). Anaerobic slurry experiments were run at different salinity treatments (0, 10, and 25) and net changes in concentration of nitrate, nitrite, ammonium, and nitrous oxide were monitored. Salinity-induced NH4+ sediment desorption was observed at all sites. No significant salinity driven changes in NO3- concentrations were observed, except for Ave estuarine sediments, where NO3- consumption increased 10 times as the salinity rose from 0 to 10. In the upper stretches of the three estuaries, N2O production increased sharply as salinity rose. Although no stimulation of N2O production was observed in higher salinity areas, the salinity-driven changes in N2O production are of major concern given the greenhouse characteristics of the gas. The global trend of decreasing freshwater discharge, and therefore increase in salinity, to estuarine systems could thereby exacerbate N2O production and global warming.

The seasonal distribution of polycyclic aromatic hydrocarbons, polychlorinated biphenyls, organochlorine pesticides, organophosphorus pesticides, triazines and other organic pollutants in surface seawater from the Mar Menor lagoon (SE Spain) was characterized from spring 2009 to winter 2010 by stir bar sorptive extraction and thermal desorption followed by capillary gas chromatography coupled to mass spectrometry (SBSE–GC–MS). The most ubiquitous pollutants were chlorpyrifos, chlortal-dimethyl, terbuthylazine, naphthalene and propyzamide throughout the year. Insecticides and herbicides were predominant in summer and spring, and fungicides were more abundant in autumn and winter. Chlorpyrifos was predominant in autumn and spring; herbicides (propyzamide, terbuthylazine and terbuthylazine-desethyl) in autumn and fungicides (flutolanil, boscalid, cyprodinil) in autumn and winter. The highest concentrations for the majority of pollutants were detected in autumn as consequence of air and surface/ground water inputs, and above all of desorption from terrigenous materials deposited in sediments by two intense flash flood events (September 2009).