Removal of paracetamol on biomass-derived activated carbon: Modeling the fixed bed breakthrough curves using batch adsorption experiments

The remediation of paracetamol (PA), an emerging contaminant frequently found in wastewater treatment plants, has been studied in the low concentration range (0.3–10 mg L−1) using as adsorbent a biomass-derived activated carbon. PA uptake of up to 100 mg g−1 over the activated carbon has been obtained, with the adsorption isotherms being fairly explained by the Langmuir model. The application of Reichemberg and the Vermeulen equations to the batch kinetics experiments allowed estimating homogeneous and heterogeneous diffusion coefficients, reflecting the dependence of diffusion with the surface coverage of PA. A series of rapid small-scale column tests were carried out to determine the breakthrough curves under different operational conditions (temperature, PA concentration, flow rate, bed length). The suitability of the proposed adsorbent for the remediation of PA in fixed-bed adsorption was proven by the high PA adsorption capacity along with the fast adsorption and the reduced height of the mass transfer zone of the columns. We have demonstrated that, thanks to the use of the heterogeneous diffusion coefficient, the proposed mathematical approach for the numerical solution to the mass balance of the column provides a reliable description of the breakthrough profiles and the design parameters, being much more accurate than models based in the classical linear driving force.

Three-dimensional model for multi-component reactive transport with variable density groundwater flow

PHWAT is a new model that couples a geochemical reaction model (PHREEQC-2) with a density-dependent groundwater flow and solute transport model (SEAWAT) using the split-operator approach. PHWAT was developed to simulate multi-component reactive transport in variable density groundwater flow. Fluid density in PHWAT depends not on only the concentration of a single species as in SEAWAT, but also the concentrations of other dissolved chemicals that can be subject to reactive processes. Simulation results of PHWAT and PHREEQC-2 were compared in their predictions of effluent concentration from a column experiment. Both models produced identical results, showing that PHWAT has correctly coupled the sub-packages. PHWAT was then applied to the simulation of a tank experiment in which seawater intrusion was accompanied by cation exchange. The density dependence of the intrusion and the snow-plough effect in the breakthrough curves were reflected in the model simulations, which were in good agreement with the measured breakthrough data. Comparison simulations that, in turn, excluded density effects and reactions allowed us to quantify the marked effect of ignoring these processes. Next, we explored numerical issues involved in the practical application of PHWAT using the example of a dense plume flowing into a tank containing fresh water. It was shown that PHWAT could model physically unstable flow and that numerical instabilities were suppressed. Physical instability developed in the model in accordance with the increase of the modified Rayleigh number for density-dependent flow, in agreement with previous research. (c) 2004 Elsevier Ltd. All rights reserved.

Effects of Soil Compaction and Organic Carbon Content on Preferential Flow in Loamy Field Soils

Abstract: Preferential flow and transport through macropores affect plant water use efficiency and enhance leaching of agrochemicals and the transport of colloids, thereby increasing the risk for contamination of groundwater resources. The effects of soil compaction, expressed in terms of bulk density (BD), and organic carbon (OC) content on preferential flow and transport were investigated using 150 undisturbed soil cores sampled from 15 × 15–m grids on two field sites. Both fields had loamy textures, but one site had significantly higher OC content. Leaching experiments were conducted in each core by applying a constant irrigation rate of 10 mm h−1 with a pulse application of tritium tracer. Five percent tritium mass arrival times and apparent dispersivities were derived from each of the tracer breakthrough curves and correlated with texture, OC content, and BD to assess the spatial distribution of preferential flow and transport across the investigated fields. Soils from both fields showed strong positive correlations between BD and preferential flow. Interestingly, the relationships between BD and tracer transport characteristics were markedly different for the two fields, although the relationship between BD and macroporosity was nearly identical. The difference was likely caused by the higher contents of fines and OC at one of the fields leading to stronger aggregation, smaller matrix permeability, and a more pronounced pipe-like pore system with well-aligned macropores.

Inferring transport characteristics in a fractured rock aquifer by combining single-hole ground-penetrating radar reflection monitoring and tracer test data

Investigations of solute transport in fractured rock aquifers often rely on tracer test data acquired at a limited number of observation points. Such data do not, by themselves, allow detailed assessments of the spreading of the injected tracer plume. To better understand the transport behavior in a granitic aquifer, we combine tracer test data with single-hole ground-penetrating radar (GPR) reflection monitoring data. Five successful tracer tests were performed under various experimental conditions between two boreholes 6 m apart. For each experiment, saline tracer was injected into a previously identified packed-off transmissive fracture while repeatedly acquiring single-hole GPR reflection profiles together with electrical conductivity logs in the pumping borehole. By analyzing depth-migrated GPR difference images together with tracer breakthrough curves and associated simplified flow and transport modeling, we estimate (1) the number, the connectivity, and the geometry of fractures that contribute to tracer transport, (2) the velocity and the mass of tracer that was carried along each flow path, and (3) the effective transport parameters of the identified flow paths. We find a qualitative agreement when comparing the time evolution of GPR reflectivity strengths at strategic locations in the formation with those arising from simulated transport. The discrepancies are on the same order as those between observed and simulated breakthrough curves at the outflow locations. The rather subtle and repeatable GPR signals provide useful and complementary information to tracer test data acquired at the outflow locations and may help us to characterize transport phenomena in fractured rock aquifers.

Geological structure, recharge processes and underground drainage of a glacierised karst aquifer system, Tsanfleuron-Sanetsch, Swiss Alps

The relationships between stratigraphic and tectonic setting, recharge processes and underground drainage of the glacierised karst aquifer system `Tsanfleuron-Sanetsch' in the Swiss Alps have been studied by means of various methods, particularly tracer tests (19 injections). The area belongs to the Helvetic nappes and consists of Jurassic to Palaeogene sedimentary rocks. Strata are folded and form a regional anticlinorium. Cretaceous Urgonian limestone constitutes the main karst aquifer, overlain by a retreating glacier in its upper part. Polished limestone surfaces are exposed between the glacier front and the end moraine of 1855/1860 (Little Ice Age); typical alpine karrenfields can be observed further below. Results show that (1) large parts of the area are drained by the Glarey spring, which is used as a drinking water source, while marginal parts belong to the catchments of other springs; (2) groundwater flow towards the Glarey spring occurs in the main aquifer, parallel to stratification, while flow towards another spring crosses the entire stratigraphic sequence, consisting of about 800 m of marl and limestone, along deep faults that were probably enlarged by mass movements; (3) the variability of glacial meltwater production influences the shape of the tracer breakthrough curves and, consequently, flow and transport in the aquifer.

Separation of ammonia and carbon dioxide by adsorption

Tässä työssä on tutkittu ammoniakin ja hiilidioksidin erottamista adsorptio prosessilla ja suunniteltiin paineen muunteluun perustuvan adsorptioprosessin (PSA) käyttöä. Työn tarkoituksena oli laskea adsorptioon perustuvan prosessin kannattavuus melamiinitehtaan poistokaasujen erotuksessa. Tätä varten työssä suunniteltiin tehdasmitta-kaavainen prosessi ja arvioitiin sen kannattavuus. Työssä mitattiin adsorptiotasapainot, joiden perusteella sovitettiin sopiva kokeellinen adsorptioisotermi. Adsorptioisotermi lisättiin simulointiohjelmaan, jonka avulla suunniteltiin kaksi vaihtoehtoista pilot laitteistoa kaasujen erottamiseksi. Toisella pilot laitteistolla saadaan mitattua vain läpäisykäyrät, mutta paremmalla versiolla saadaan myös tietoa erotettujen komponenttien puhtaudesta. Suunnittelun tärkeimpiä lähtökohtia on molempien komponenttien mahdollisimman korkea puhtaus ja talteenottoaste. Täysimittakaavainen tehdas suunniteltiin simulointiohjelmiston avulla kahdelle eri kapasiteetille ja arvioitiin niiden kustannukset ja kannattavuus. Adsorptioprosessit osoittautuivat kannattaviksi kaasuseoksen erottamisessa kummassakin tapauksessa

Ammoniakin talteenottoprosessin kehitys

Diplomityössä kehitettiin ioninvaihtoon perustuva ammoniakin talteenottoprosessi NSSC (Neutral Sulphite Semi Chemical) -prosessin haihduttamon lauhteille. Tarkoituksena oli saada aallotuskartonkitehtaan kemi-kaalikiertoa suljettua ja sitä kautta ammoniakkipäästöjä vähennettyä. Ammoniakki tuli ottaa hyötymuodossa (ammoniakkihöyry tai ammoniumsulfiitti) talteen. Ammoniumsulfiittiliuosta käytetään NSSC-prosessissa keittonesteenä. Kirjallisuusosassa selvitetään strippaukseen perustuvia ammoniakin talteenottomahdollisuuksia. Tutkitaan ioninvaihdon teoriaa ja ammoniumin talteenottoon sopivien ioninvaihtomateriaalien ominaisuuksia ioninvaihtajina. Lisäksi esitetään ioninvaihtoprosesseihin liittyviä laitteistoratkaisuja ja prosessiolosuhteita. Työn kokeellisessa osassa on yleiskuvaus Powerflute Oy Savon Sellun prosesseista ja selvitetään ammoniakin merkitystä tehtaalle. Laboratoriokokein tutkittiin orgaanisten kationihartsien sekä epäorgaanisen luonnon zeoliitin soveltuvuutta ammoniumionien vaihtoon esihaihduttamon lauhteesta. Ammoniakin talteenottoprosessin toimivuutta teollisessa mittakaavassa selvitettiin rakennetulla pilotlaitteistolla suoritettujen kokeiden avulla. Lopuksi tehtiin ammoniakin talteenottoprosessin scale-up: laskettiin prosessin talteenottokapasiteetti, arvioitiin kustannuksia sekä annettiin lausunto prosessin toteutettavuudesta. Laboratoriokokeiden perusteella luonnon zeoliitti ja heikosti hapan ioninvaihtohartsi eivät sovellu ammoniumionien vaihtoon NSSC haihduttamon lauhteista. Vahvasti hapan kationihartsi toimi ammoniumin talteenotossa parhaiten, joten se valittiin pilotkokeiden ioninvaihtomateriaaliksi. Pilotkokeissa ioninvaihtomateriaaliin saatiin sidottua ammoniumia noin 30 g NH4+ / dm3 hartsia, kun materiaalin teoreettinen ioninvaihtokapasiteetti oli 32 g NH4+ / dm3 hartsia. Ammoniumin läpäisykäyrien muotoon vaikutti suuresti syöttölauhteen virtausnopeus ja ammoniumpitoisuus. Ioninvaihtomateriaalipedin syvyydellä ei ollut niinkään merkitystä. Pilotkokeiden regenerointitavoista tehokkaimmaksi osoittautui höyrystrippaus, jossa saavutettiin noin 90 %:n talteenottotehokkuus. Rikkihapokekäsittelyllä talteenottotehokkuus jäi 50 %:iin. Teollisen mittakaavan laitoksella voidaan vuosittain regenerointitavasta riippuen ottaa talteen esihaihdut-tamon lauhteesta noin 100-150 tonnia ammoniakkia. Prosessin käyttökustannukset ovat talteenotetusta ammoniakista saataviin säästöihin verrattuna suuret ja niihin vaikuttaa merkittävästi ioninvaihtohartsin käyttöikä sekä regenerointikemikaalien kulutus. Osittaisella kemikaalikierron sulkemisella saavutetaan NSSC-prosessissa sekundäärietuja, joiden vaikutuksen merkittävyys pitäisi tarkentaa lisätutkimuksilla.

Lämpötilan vaikutus kuparin ja nikkelin kolonnierotuksessa kelatoivalla adsorbentilla

Sinkin valmistuksessa pitää sinkkirikasteesta poistaa epäpuhtausmetallit ennen elektrolyysiä. Nykyisin epäpuhtauksien poistamiseksi käytetään sementointimene-telmiä. Sementointi voisi olla mahdollista korvata kelatoivalla adsorbentilla suori-tettavalla erotuksella, jonka etuja ovat selektiivisyys ja ympäristöystävällisyys. Työn tarkoituksena on tutkia lämpötilan vaikutusta kelatoivalla adsorbentilla teh-tävään nikkelin ja kuparin kolonnierotukseen. Kolonnierotuksessa lämpötila voi vaikuttaa sekä liuoksen että adsorbentin fysi-kaalisiin, kemiallisiin ja sähkökemiallisiin ominaisuuksiin. Näiden vaikutusten johdosta voivat esimerkiksi erotuksen stoikiometria, kinetiikka tai toimintaolosuh-teet muuttua. Tässä työssä lämpötilan vaikutusta kolonnierotukseen tutkittiin rik-kihapon ja erotusmateriaalin välisillä kinetiikkakokeilla sekä synteettisellä CuSO4-liuoksella ja autenttisella ZnSO4-liuoksella tehdyillä kolonniajoilla. Työssä käytetyn erotusmateriaalin runko on silikapolyamiini ja sen funktionaali-sena ryhmänä toimii 2-aminometyylipyridiini. Lämpötilan ollessa 60 °C havaittiin erotusmateriaalin ja rikkihapon asettuvan tasapainoon kolme kertaa nopeammin kuin 25 °C:ssa. Lämpötilan nostamisella edelleen 90 °C:een ei havaittu olevan merkittävää vaikutusta tasapainon saavuttamisen nopeuteen. Kuparin läpäisykäyrän havaittiin jyrkentyvän lämpötilan noston vaikutuksesta niin autenttisella ZnSO4-liuoksella kuin synteettisellä CuSO4-liuoksella. Tämän oletettiin johtuvan kinetiikan nopeuden kasvusta sekä autenttisella liuoksella myös viskositeetin pienenemisestä. Lämpötilan vaikutuksesta on mahdollista käsitellä autenttista ZnSO4-liuosta 90 °C:ssa noin 3,5-kertaa enemmän kuin 25 °C:ssa, siten että liuoksesta saadaan poistettua lähes kaikki kupari. Nikkelin havaittiin lä-päisevän kolonnin kaikissa lämpötiloissa lähes välittömästi. Tästä syystä tutkittu erotusmateriaali ei sovellu nikkelin ja kuparin samanaikaiseen erottamiseen tutki-tusta autenttisesta ZnSO4-liuoksesta.

Temperature effect in potassium and nitrate ions in soil transport

When doing researches on solute dynamics in porous medium, the knowledge of medium characteristics and percolating liquids, as well as of external factors is very important. An important external factor is temperature and, in this sense, our purpose was determining potassium and nitrate transport parameters for different values of temperature, in miscible displacement experiments. Evaluated parameters were retardation factor (R), diffusion/dispersion coefficient (D) and dispersivity, at ambient temperature (25 up to 28 ºC), 40 ºC and 50 ºC. Salts used were potassium nitrate and potassium chlorate, prepared in a solution made up of 5 ppm nitrate and 2.000 ppm potassium, with Red-Yellow Latosol porous medium. Temperature exhibited a positive influence upon porous medium solution and upon dispersion coefficient.

Avaliação do modelo HYDRUS-1D na simulação do transporte de água e potássio em colunas preenchidas com solos tropicais

A preocupação com o destino de produtos químicos e água, aplicados ao solo, tem motivado vários pesquisadores a desenvolverem e aplicarem modelos teóricos, a fim de descrever os processos físicos envolvidos no transporte desses produtos no perfil do solo. Nesse sentido, esta pesquisa teve como objetivo aplicar o modelo HYDRUS-1D, bem como avaliar sua performance, em simulações do deslocamento do potássio e água (umidade do solo), em colunas segmentadas, preenchidas com dois tipos de solos tropicais, em condições não saturadas (Latossolo Vermelho- - Amarelo e Nitossolo Vermelho). Os parâmetros de transporte do potássio foram obtidos por meio de curvas de distribuição de efluentes (Breakthrough Curves (BTC)). O desempenho do modelo foi avaliado com base nos seguintes parâmetros estatísticos: erro máximo, erro absoluto médio, raiz quadrada do erro médio normalizado, coeficiente de massa residual, coeficiente de determinação, eficiência e índice de concordância de Willmott. Diante dos resultados obtidos, pôde-se concluir que o modelo HYDRUS-1D foi eficiente nas simulações de deslocamento do potássio e da água, em relação aos dois materiais de solo estudados.

Effect of companion ion on nitrate displacement through transport parameters analysis

Nitrate is the main form of nitrogen associated with water contamination; the high mobility of this species in soil justifies the concern regarding nitrogen management in agricultural soils. Therefore, the objective of this research was to assess the effect of companion cation on nitrate displacement, by analyzing nitrate transport parameters through Breakthrough Curves (BTCs) and their settings made by numerical model (STANMOD). The experiment was carried out in the Soil and Water Quality Laboratory of the Department of Biosystems Engineering, "Luiz de Queiroz" College of Agriculture in Piracicaba (SP), Brazil. It was performed using saturated soil columns in steady-state flow condition, in which two different sources of inorganic nitrate Ca(NO3)2 and NH4NO3 were applied at a concentration of 50 mg L-1 NO3-. Each column was filled with either a Red-Yellow Oxisol (S1) or an Alfisol (S2). Results are indicative that the companion ion had no effect on nitrate displacement. However, nitrate transport was influenced by soil texture, particle aggregation, solution speed in soil and organic matter presence. Nitrate mobility was higher in the Alfisol (S2).

Novel technology for preparation of optically active chemicals

Asymmetric synthesis using modified heterogeneous catalysts has gained lots of interest in the production of optically pure chemicals, such as pharmaceuticals, nutraceuticals, fragrances and agrochemicals. Heterogeneous modified catalysts capable of inducing high enantioselectivities are preferred in industrial scale due to their superior separation and handling properties. The topic has been intensively investigated both in industry and academia. The enantioselective hydrogenation of ethyl benzoylformate (EBF) to (R)-ethyl mandelate over (-)-cinchonidine (CD)-modified Pt/Al2O3 catalyst in a laboratory-scale semi-batch reactor was studied as a function of modifier concentration, reaction temperature, stirring rate and catalyst particle size. The main product was always (R)-ethyl mandelate while small amounts of (S)-ethyl mandelate were obtained as by product. The kinetic results showed higher enantioselectivity and lower initial rates approaching asymptotically to a constant value as the amount of modifier was increased. Additionally, catalyst deactivation due to presence of impurities in the feed was prominent in some cases; therefore activated carbon was used as a cleaning agent of the raw material to remove impurities prior to catalyst addition. Detailed characterizations methods (SEM, EDX, TPR, BET, chemisorption, particle size distribution) of the catalysts were carried out. Solvent effects were also studied in the semi-batch reactor. Solvents with dielectric constant (e) between 2 and 25 were applied. The enantiomeric excess (ee) increased with an increase of the dielectric coefficient up to a maximum followed by a nonlinear decrease. A kinetic model was proposed for the enantioselectivity dependence on the dielectric constant based on the Kirkwood treatment. The non-linear dependence of ee on (e) successfully described the variation of ee in different solvents. Systematic kinetic experiments were carried out in the semi-batch reactor. Toluene was used as a solvent. Based on these results, a kinetic model based on the assumption of different number of sites was developed. Density functional theory calculations were applied to study the energetics of the EBF adsorption on pure Pt(1 1 1). The hydrogenation rate constants were determined along with the adsorption parameters by non-linear regression analysis. A comparison between the model and the experimental data revealed a very good correspondence. Transient experiments in a fixed-bed reactor were also carried out in this work. The results demonstrated that continuous enantioselective hydrogenation of EBF in hexane/2-propanol 90/10 (v/v) is possible and that continuous feeding of (-)-cinchonidine is needed to maintain a high steady-state enantioselectivity. The catalyst showed a good stability and high enantioselectivity was achieved in the fixed-bed reactor. Chromatographic separation of (R)- and (S)-ethyl mandelate originating from the continuous reactor was investigated. A commercial column filled with a chiral resin was chosen as a perspective preparative-scale adsorbent. Since the adsorption equilibrium isotherms were linear within the entire investigated range of concentrations, they were determined by pulse experiments for the isomers present in a post-reaction mixture. Breakthrough curves were measured and described successfully by the dispersive plug flow model with a linear driving force approximation. The focus of this research project was the development of a new integrated production concept of optically active chemicals by combining heterogeneous catalysis and chromatographic separation technology. The proposed work is fundamental research in advanced process technology aiming to improve efficiency and enable clean and environmentally benign production of enantiomeric pure chemicals.

Zur Adsorption und Reaktion von Stickstoffmonoxid an Aktivkohle

Die Verwendung von Aktivkohlen und -koksen stellt eine Alternative zu herkömmlichen Prozessen zur Verminderung der NOx-Emissionen in Rauchgasen dar. An diesen Materialien wird Stickstoffmonoxid adsorbiert und katalytisch zu N2 reduziert. Eine einheitliche Erklärung über die ablaufenden Vorgänge und die Reaktionsmechanismen gibt es noch nicht. Die Ergebnisse der bisher veröffentlichten wissenschaftlichen Arbeiten sind sehr unterschiedlich, wenn nicht sogar widersprüchlich. In dieser Arbeit wird, anhand der Messung von NO-Durchbruchskurven und thermischen Desorptionsspektren, die Adsorption und Reaktion von Stickstoffmonoxid an Aktivkohlen und -koksen in Anwesenheit von Sauerstoff und Wasserdampf untersucht. Zur Durchführung der experimentellen Untersuchungen wird eine Versuchsanlage, bestehend aus einer Vorrichtung zur Gasgemischaufbereitung, einem Festbettreaktor und einer Gasanalytik, konzipiert und aufgebaut. Die Untersuchungen erfolgen bei Temperaturen zwischen 100 und 150 °C. Die NO-, O2- und H2O-Konzentrationen werden anhand der Rauchgaszusammensetzung kohlegefeuerter Kraftwerke gewählt. Die experimentellen Untersuchungen konzentrieren sich auf die Verwendung einer Aktivkohle aus Ölpalmschalen, die in einem Drehrohrreaktor am Institut für Thermische Energietechnik der Universität Kassel hergestellt wurde. Die experimentellen Ergebnisse zeigen, dass während des Prozesses NO-Adsorption, -Reduktion und -Oxidation, NO2-Bildung, -Adsorption und -reduktive Desorption, H2O-Adsorption sowie O2-Vergasung gleichzeitig stattfinden. Bei niedrigen Temperaturen werden die NO2-Bildung und die Adsorption bevorzugt. Die NO-Reduktion läuft über adsorbiertes NO mit CO2- und CO-Bildung. Durch O2-Vergasung werden aktive freie Cf-Plätzen für die NO-Reaktion und -Adsorption gebildet. Wasserdampf wird an der Aktivkohle adsorbiert und belegt aktive Plätze für diese Prozesse. Aus den experimentellen Ergebnissen werden kinetische und Gleichgewichtsparameter der NO-Sorption bestimmt. Ein vereinfachtes mathematisches Modell des Festbettreaktors, das zur Berechnung der NO-Durchbruchskurven bei unterschiedlichen Temperaturen dient, wird aufgestellt.

Prediction leaching of potassium using the convective-dispersive and the convective log-normal transfer function models

There is increasing concern about soil enrichment with K+ and subsequent potential losses following long-term application of poor quality water to agricultural land. Different models are increasingly being used for predicting or analyzing water flow and chemical transport in soils and groundwater. The convective-dispersive equation (CDE) and the convective log-normal transfer function (CLT) models were fitted to the potassium (K+) leaching data. The CDE and CLT models produced equivalent goodness of fit. Simulated breakthrough curves for a range of CaCl2 concentration based on parameters of 15 mmol l(-1) CaCl2 were characterised by an early peak position associated with higher K+ concentration as the CaCl2 concentration used in leaching experiments decreased. In another method, the parameters estimated from 15 mmol l(-1) CaCl2 solution were used for all other CaCl2 concentrations, and the best value of retardation factor (R) was optimised for each data set. A better prediction was found. With decreasing CaCl2 concentration the value of R is required to be more than that measured (except for 10 mmol l(-1) CaCl2), if the estimated parameters of 15 mmol l(-1) CaCl2 are used. The two models suffer from the fact that they need to be calibrated against a data set, and some of their parameters are not measurable and cannot be determined independently.

Solute movement through intact columns of cryoturbated Upper Chalk

Cryoturbated Upper Chalk is a dichotomous porous medium wherein the intra-fragment porosity provides water storage and the inter-fragment porosity provides potential pathways for relatively rapid flow near saturation. Chloride tracer movement through 43 cm long and 45 cm diameter undisturbed chalk columns was studied at water application rates of 0.3, 1.0, and 1.5 cm h(-1). Microscale heterogeneity in effluent was recorded using a grid collection system consisting of 98 funnel-shaped cells each 3.5 cm in diameter. The total porosity of the columns was 0.47 +/- 0.02 m(3) m(-3), approximately 13% of pores were >15 mu m diameter, and the saturated hydraulic conductivity was 12.66 +/- 1.31 m day(-1). Although the column remained unsaturated during the leaching even at all application rates, proportionate flow through macropores increased as the application rate decreased. The number of dry cells (with 0 ml of effluent) increased as application rate decreased. Half of the leachate was collected from 15, 19 and 22 cells at 0.3, 1.0, 1.5 cm h(-1) application rates respectively. Similar breakthrough curves (BTCs) were obtained at all three application rates when plotted as a function of cumulative drainage, but they were distinctly different when plotted as a function of time. The BTCs indicate that the columns have similar drainage requirement irrespective of application rates, as the rise to the maxima (C/C-o) is almost similar. However, the time required to achieve that leaching requirement varies with application rates, and residence time was less in the case of a higher application rate. A two-region convection-dispersion model was used to describe the BTCs and fitted well (r(2) = 0.97-0-99). There was a linear relationship between dispersion coefficient and pore water velocity (correlation coefficient r = 0.95). The results demonstrate the microscale heterogeneity of hydrodynamic properties in the Upper Chalk. Copyright (C) 2007 John Wiley & Sons, Ltd.