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.

This study evaluated the dietary uptake kinetics and sublethal toxicity of p,p′-dichlorodiphenyl dichloroethylene (p,p′-DDE) in Antarctic krill. The uptake rate constant (characterised by the seawater volume stripped of contaminant sorbed to algae) of 200 ± 0.32 mL g−1 wet weight h−1, average absorption efficiency of 86 ± 13% and very low elimination rate constant of 5 × 10−6 ± 0.0031 h−1 demonstrate the importance of feeding for p,p′-DDE bioaccumulation in Antarctic krill. Faecal egestion of unabsorbed p,p′-DDE of 8.1 ± 2.7% indicates that this pathway contributes considerably to p,p′-DDE sinking fluxes. A median internal effective concentration (IEC50) of 15 mmol/kg lipid weight for complete immobility indicates baseline toxicity and that Antarctic krill exhibit comparable toxicological sensitivity as temperate species under similar 10 d exposure conditions. These findings support the critical body residue approach and provide insight to the role of Antarctic krill in the biogeochemical cycling of p,p′-DDE in the Southern Ocean.

The aim of this study was to improve our understanding of metal bioavailability in soil by linking the biotic ligand approach with toxicokinetics modelling. We determined cadmium bioaccumulation kinetics in Folsomia candida (Collembola) as a function of soil pH. Animals were exposed for 21 days to LUFA 2.2 soil at 5 or 20 μg Cd g−1 dry soil followed by 21 days elimination in clean soil. Internal cadmium concentrations were modelled using a first-order one-compartment model, relating uptake rate constants (k1) to total soil, water or 0.01 M CaCl2 extractable and porewater concentrations. Based on total soil concentrations, k1 was independent of soil pH while it strongly increased with increasing pH based on porewater concentrations explaining the reduced competition of H+ ions making cadmium more bioavailable in pore water at high pH. This shows that the principles of biotic ligand modelling are applicable to predict cadmium accumulation kinetics in soil-living invertebrates.

Covalent coupling to natural humic constituents comprises an important transformation pathway for anilinic pollutants in the environment. We systematically investigated the reactions of chlorine substituted anilines with catechol and syringic acid in horseradish peroxidase (HRP) catalyzed systems. It was demonstrated that although nucleophilic addition was the mechanism of covalent bonding to both catechol and syringic acid, chloroanilines coupled to the 2 humic constituents via slightly different pathways. 1,4-addition and 1,2-addition are involved to catechol and syringic acid, respectively. 1,4-addition showed empirical 2nd order kinetics and this pathway seemed to be more permanent than 1,2-addition. Stability experiments demonstrated that cross-coupling products with syringic acid could be easily released in acidic conditions. However, cross-coupling with catechol was relatively stable at similar conditions. Thus, the environmental behavior and bioavailability of the coupling products should be carefully assessed.

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.

Egypt is a major agricultural country in Africa with a known past of organochlorine pesticides (OCPs) application, yet data on atmospheric levels of OCPs in Egypt is sparse. Low density polyethylene (LDPE) passive samplers were therefore deployed for 3 weeks each at 11 locations in July, 2010 and January, 2011 in Alexandria to screen for gas-phase OCPs. Performance reference compounds were used to investigate the uptake kinetics. Field-derived sampler-air partitioning coefficients (KPE-As) for OCPs were significantly correlated against the compounds' subcooled liquid vapor pressure (log PL): [log KPE-A = −0.77 ± 0.07*log PL + 6.35 ± 0.13 (R2 = 0.90; n = 17; SE = 0.19; p < 0.001)]. Estimated and measured OCP concentrations in Alexandria agreed well (factor difference ≤ 2) indicating the feasibility of monitoring OCPs using LDPEs. OCP concentrations ranged from <LOD to 168 pg/m3. Calculated isomeric ratios indicated recent usage of chlordanes and endosulfans.

The long-term environmental fate of the veterinary antibiotic sulfadiazine (SDZ) in soils is determined by a reversible sequestration into a residual fraction and an irreversible formation of non-extractable residues (NER), which can be described as first-order rate processes. However, the concentration dynamics of the resulting fractions of SDZ in soil show an unexplained rapid reduction of extractability during the first 24 h. We therefore investigated the short-term extractability of SDZ in two different soils under different SDZ application procedures over 24 h: with and without manure, for air-dried and for moist soils. In all batches, we observed an instantaneous loss of extractability on a time scale of minutes as well as kinetically determined sequestration and NER formation over 24 h. Data evaluation with a simple kinetic model led to the conclusion that application with manure accelerated the short-term formation of NER, whereas sequestration was very similar for all batches.

Mass transfer processes of pollutants from non-aqueous phase liquids (NAPL) may control groundwater pollution at abandoned industrial sites. We studied release kinetics of polycyclic aromatic hydrocarbons (PAHs) from fresh and aged tar phases using a dialysis tubing technique. Time for equilibration ranged from several days to more than three years. For fresh tar materials the release seems to be limited by retarded pore diffusion, while for two of three aged tars diffusion limited release influenced by dissolved organic matter (DOM) was assumed. The equilibration process was driven by solubilization thermodynamics expressed by Raoult's law. Yet, solubility enhancement was observed potentially due to the presence of organic mobile sorbents. The results show that the release of PAHs from tar phases is generally rate limited and partitioning according to Raoult's law is the driving mechanism of the exchanges process.

Freeze–thaw cycling may influence the chemistry, mineral stability and reaction rate during metal orthophosphate fixation. This study assessed the formation and stability of Cu-, Pb-, and Zn-phosphates in chemically simple laboratory systems during 240 freeze–thaw cycles (120 days) from +10 to −20 °C, using X-ray diffractometry. In single heavy metal systems, chloro- and hydroxy-pyromorphite (Pb5(PO4)3(Cl,OH)), sodalite (Na6Zn6(PO4)6·8H2O), chiral zincophosphate (Na12(Zn12P12O48)·12H2O), and copper phosphate hydrate (Cu3(PO4)2·3H2O) were the primary phosphate minerals that formed, and were typically stable during the experiment. Zinc and Cu-phosphate formation was reduced in multi heavy metal systems, and was substantially lower in abundance than chloropyromorphite. Successful Cu-, Pb- and Zn-phosphate formation can be expected in cold and freezing environments like the polar regions. However, field implementation of orthophosphate fixation needs to consider competing ion effects, concentration of the phosphate source, and the amount of free-water.

The significance of biofilm on the transport and deposition behaviors of ZnO nanoparticles were examined under a series of environmentally relevant ionic strength at two fluid velocities of 4 m-d−1 and 8 m-d−1. Biofilm enhanced nanoparticles retention in porous media under all examined conditions. The greater deposition was also observed in extracellular polymeric substances (EPS) coated surfaces by employment of quartz microbalance with dissipation (QCM-D) system. Derjaguin–Landau–Verwey–Overbeek (DLVO) failed to interpret more ZnO nanoparticles deposition on biofilm (EPS) coated silica surfaces. Chemical interaction and physical morphology of biofilm contributed to this greater deposition (retention). Biofilm affected the spacial distribution of retained ZnO nanoparticles as well. Relatively steeper slope of retained profiles were observed in the presence of biofilm, corresponding to the greater deviation from colloid filtration theory (CFT). Pore space constriction via biofilm induced more nanoparticle trapped in the column inlet, leading to greater deviations (σln kf) from the CFT.