Laboratory studies were conducted to characterise the sorption-desorption behavior of four human pharmaceuticals (carbamazepine, diclofenac, gemfibrozil, and ibuprofen) at three initial concentrations in aqueous solution on one river sediment. The results of the experiments showed that distribution coefficients were either relatively low for diclofenac and ibuprofen or higher for gemfibrozil and carbamazepine. Distribution coefficients (mean Kd values for three initial concentrations), as measured by the batch experiments, were 4.21 ± 0.58 for diclofenac, 4.98 ± 0.29 for ibuprofen, 11.28 ± 1.22 for gemfibrozil, and 44.82 ± 14.89 for carbamazepine. Based on sorption data, migration potential of the pharmaceuticals in surface waters would decrease as follows: diclofenac > ibuprofen > gemfibrozil >> carbamazepine. Only 2.44 ± 1.05%, 3.67 ± 0.35% and 1.79 ± 1.17% of the initially sorbed ibuprofen, gemfibrozil and carbamazepine were desorbed during desorption period of 48 h, respectively. Diclofenac exhibited the highest desorption (15.01 ± 2.59%). Generally, the results indicate that significant amounts of the pharmaceuticals may be eliminated from surface waters via sorption by sediment and that observed low desorption would further limit their migration in surface waters.

Burning of crop residues in the fields is a routine post-harvest practice and results in accumulation of ashes in soils. Recent studies have shown that the ashes may significantly contribute to the herbicide sorption in soils. This study was conducted to evaluate the potential role of wheat ash in immobilization of anionic herbicide MCPA in soils. The results showed that wheat ash is highly effective sorbent for herbicide MCPA. Amendment of Fluvi-Gleyic Phaeozem and Eutric Regosol with 1% wheat ash caused a 8-fold and 16-fold increase in MCPA sorption, respectively. Desorption of MCPA was also influenced by wheat ash in soils. The addition of wheat ash to both soils increased the resistant fraction to desorption up to 80%. Generally, the field burning of crop residues appears to increase the sorption of pesticides in agricultural soils and decrease their leaching.

Acidic herbicide MCPA (4-chloro-2-methylphenoxyacetic acid) is applied to post-emergence control of annual and perennial broad-leaved weeds, mostly in cereals. This study was undertaken with two soils of different properties sampled from two soil horizons to determine the extent of degradation, sorption and desorption of MCPA. These processes are the most important to evaluate the fate of the herbicide in soil and its potential to leach from soil into groundwater. Two soils were used: a calcareous, sandy-loam soil with organic carbon content of 2.486 % (Pararendzina) taken from surface A horizon (the A topsoil) and a calcareous, loamy-sand soil with organic C content of 0.600 % (Fluvisol) sampled from subsurface C horizon (the C subsoil). The extent of degradation, sorption and desorption of MCPA were measured in laboratory batch experiments. Degradation followed first-order kinetics, with the MCPA half-lives of 11 and 24 d for the A topsoil and C subsoil, respectively. Soil organic carbon influenced MCPA degradation. Sorption followed a Freundlich isotherm equation and linear isotherm equation, as well. The distribution coefficient KD was higher in the A topsoil (0.387 l kg-1) than in the C subsoil (0.165 l kg-1), consistent with the higher organic C content of the A soil. The results indicate that MCPA is potentially mobile and might pose a threat to future groundwater quality due to its low sorption, relatively high water solubility and slow degradation in the C subsoil.

MCPA sorption and desorption in five surface sods (denoted as A1-5), three bottom sediments (S1-3), two river sediments (L1-2) and one subsurface sod (SS) at two initial concentrations in aqueous solution - C-0 = 0.5 and 10 mg/l were studied. No significant effect of the initial concentration on MCPA equilibrium distribution between soil/sediment and aqueous solution was observed, The difference between distribution coefficient K-D at C-0 = 0.5 mg/l and K-D at C-0 = 10 mg/l was found only in the case of one bottom sediment (S2). A simple regression analysis between K-D at C-0 = 0.5 and 10 mg/l and soil/sediment properties indicated that the most important property which determined the variation in MCPA sorption is organic carbon (r = 0.886*** and r = 0.926***, respectively). Similarly, desorption of MCPA was inversely proportional to organic carbon content of the sods and sediments used (r = -0.862* and r = -0.842**). These observations showed that MCPA sorption and desorption in soils and sediments were primarily controlled by organic components of the geosorbents used. Overall, the percentage of MCPA sorption in soils and sediments was low (P-sorp approximate to 3-53%; K-D = 0.077-2.827 l/kg) and the percentage of MCPA desorbed was relatively high (P-des approximate to 11-70%), especially in the sods and sediments with lower organic carbon content. The experimental results and calculated values of groundwater ubiquity score GUS and relative leaching potential index RLPI imply that MCPA is very mobile in all the surface sods and has a potential to contaminate groundwater.

This study is dedicated to laboratory investigation of sorption behavior of polycyclic aromatic hydrocarbons in soils under equilibrium and non-equilibrium conditions. Six soils from Slovakia with different organic carbon fraction (fOC = 0.0048–0.0241), clay fraction (fCM = 0.006–0.372) and mineralogical composition of clays were used for determination of naphthalene, acenaphthene, fluorene, phenanthrene and pyrene sorption isotherms. Impact of sorption contact time on sorption behavior of studied PAHs was evaluated by measured distribution relationships S(t) vs. C(t) for naphthalene, phenanthrene and pyrene in one soil sample at contact time of 2 hours, 1 day, 2 days (3 for pyrene) and 21 days. The experimental sorption isotherms were nonlinear and fitted very well with the Freundlich adsorption isotherm: S = KFCeN over a range of used aqueous phase PAH concentrations. The more detailed analysis of results showed that soil organic carbon was predominant sorbent in the sorption of investigated polycyclic aromatic hydrocarbons from aqueous solution by soils, although it was found that sorption behavior of PAH compounds in soils was significantly affected by smectites when organic carbon/smectite ratio was roughly below 0.1 (fOC/fsmectite ~0.1). The results also showed that average distribution coefficient KD values and the normalized to organic carbon content KOC of studied PAH compounds, despite observed nonlinear sorption, were comparable with their values earlier published in the literature and were dependent on their molecular properties: hydrophobicity expressed as KOW and water solubility SW. All observed distribution relationships for contact times used fitted to a power function reflecting non-equilibrium conditions: S(t) = kF(t)C(t)n(t). The data indicate significant increase in sorption of naphthalene between 2 h and 1 d, phenanthrene between 2 h and 2 d and pyrene at interval of 2 h to 21 d. This observation suggests that more hydrophobic PAH compounds exhibit slower sorption kinetics than less hydrophobic compounds like naphthalene. Observed changes in sorption of PAHs studied as contact time increased indicate that literature KD and KOC values for many organic compounds can be significantly underestimated as were measured over short periods (?1 d) because short periods not need always represent equilibrium conditions during realized batch experiments.

We investigated the sorption-desorption behaviour of acid herbicide MCPA (4-chloro-2-methylphenoxy acetic acid) in five soils (denoted as A1-5), three bottom sediments (S1-3) and in two river sediments (L1-2) at two initial concentrations in aqueous solution – C0 = 0.5 and 10 mg L-1. Sorption and desorption of MCPA was measured by a batch equilibrium technique using analytical pure MCPA. There was no significant influence of the initial concentration of MCPA on its equilibrium distribution between soil/sediment and aqueous solution. The difference between distribution coefficient KD at C0 = 0.5 mg L-1 and KD at C0 = 10 mg L-1 was found only in the case of one bottom sediment (S2). Simple regression analysis between KD at C0 = 0.5 and 10 mg L-1 and soil/sediment properties indicated that the most important property which determined the variation in MCPA sorption is organic carbon (r = 0.885** and r = 0.921***, respectively). Similarly, the desorption of MCPA was inversely proportional to organic carbon content of the soils and sediments used (r = –0.821* and r = –0.888**). These observations showed that sorption-desorption behaviour of MCPA in soils and sediments was primarily controlled by organic components of the geosorbents used. Overall, the sorption extent of MCPA in soils and sediments was low (P sorp ≈ 5 – 53 %; KD = 0.131 – 2.827 L kg-1) and desorption extent was relatively high (P des ≈ 11 – 52 %), especially in soils and sediments with the lower organic carbon content. The experimental results and calculated values of groundwater ubiquity score GUS and relative leaching potential index RLPI imply that MCPA is very mobile in all soils and has high potential to contaminate groundwater.