Concurrent self-assembly of RGB microLEDs for next-generation displays.

MicroLED displays have been in the spotlight as the next-generation displays owing to their various advantages, including long lifetime and high brightness compared with organic light-emitting diode (OLED) displays. As a result, microLED technology1,2 is being commercialized for large-screen displays such as digital signage and active R&D programmes are being carried out for other applications, such as augmented reality3, flexible displays4 and biological imaging5. However, substantial obstacles in transfer technology, namely, high throughput, high yield and production scalability up to Generation 10+ (2,940 × 3,370 mm2) glass sizes, need to be overcome so that microLEDs can enter mainstream product markets and compete with liquid-crystal displays and OLED displays. Here we present a new transfer method based on fluidic self-assembly (FSA) technology, named magnetic-force-assisted dielectrophoretic self-assembly technology (MDSAT), which combines magnetic and dielectrophoresis (DEP) forces to achieve a simultaneous red, green and blue (RGB) LED transfer yield of 99.99% within 15 min. By embedding nickel, a ferromagnetic material, in the microLEDs, their movements were controlled by using magnets, and by applying localized DEP force centred around the receptor holes, these microLEDs were effectively captured and assembled in the receptor site. Furthermore, concurrent assembly of RGB LEDs were demonstrated through shape matching between microLEDs and receptors. Finally, a light-emitting panel was fabricated, showing damage-free transfer characteristics and uniform RGB electroluminescence emission, demonstrating our MDSAT method to be an excellent transfer technology candidate for high-volume production of mainstream commercial products.

Response of soil microbial communities to petroleum hydrocarbons at a multi-contaminated industrial site in Lanzhou, China.

Total petroleum hydrocarbon (TPH) contamination poses threats to ecological systems and human health. Many studies have reported its negative impacts on soil microbes, but limited information is known about microbial change and response to multiple TPH contamination events. In this study, we investigated TPH contamination level, microbial community structure and functional genes at a multi-contaminated industrial site in Lanzhou, where a benzene spill accident caused the drinking water crisis in 2014. TPHs distribution in soils and groundwater indicated multiple TPH contamination events in history, and identified the spill location where high TPH level (6549 mg kg-1) and high ratio of low-molecular-weight TPHs (>80%) were observed. In contrast, TPH level was moderate (349 mg kg-1) and the proportion of low-molecular-weight TPHs was 44% in soils with a long TPH contamination history. After the spill accident, soil bacterial communities became significant diverse (p = 0.047), but the dominant microbes remained the same as Pseudomonadaceae and Comamonadaceae. The abundance of hydrocarbon-degradation related genes increased by 10-1000 folds at the site where the spill accident occurred in multi-contaminated areas and was significantly related to 2-ring PAHs. Such changes of microbial community and hydrocarbon-degradation related genes together indicated the resilience of soil indigenous microbes toward multiple contamination events. Our results proved the significant change of bacterial community and huge shift of hydrocarbon-degradation related genes after the spill accident (multiple contamination events), and provided a deep insight into microbial response at industrial sites with a long period of contamination history.

Manipulation of Unfrozen Water Retention for Enhancing Petroleum Hydrocarbon Biodegradation in Seasonally Freezing and Frozen Soil.

Manipulating the retention of unfrozen water in freezing contaminated soil to achieve prolonged bioremediation in cold climates remains unformulated. This freezing-induced biodegradation experiment shows how nutrient and zeolite amendments affect unfrozen water retention and hydrocarbon biodegradation in field-aged, petroleum-contaminated soils undergoing seasonal freezing. During soil freezing at a site-specific rate (4 to -10 °C and -0.2 °C/d), the effect of nutrients was predominant during early freezing (4 to -5 °C), alleviating the abrupt soil-freezing stress near the freezing-point depressions, elevating alkB1 gene-harboring populations, and enhancing hydrocarbon biodegradation. Subsequently, the effect of increased unfrozen water retention associated with added zeolite surface areas was critical in extending hydrocarbon biodegradation to the frozen phase (-5 to -10 °C). A series of soil-freezing characteristic curves with empirical α-values (soil-freezing index) were constructed for the tested soils and shown alongside representative curves for clays to sands, indicating correlations between α-values and nutrient concentrations (soil electrical conductivity), zeolite addition (surface area), and hydrocarbon biodegradation. Heavier hydrocarbons (F3: C16-C34) notably biodegraded in all treated soils (22-37% removal), as confirmed by biomarker-based analyses (17α(H),21ß(H)-hopane), whereas lighter hydrocarbons were not biodegraded. Below 0 °C, finer-grained soils (high α-values) can be biostimulated more readily than coarser-grained soils (low α-values).

Sodium adsorption by reusable zeolite adsorbents: integrated adsorption cycles for salinised groundwater treatment.

Using Canadian (CMZ), Bear River (BRZ), and St. Cloud (SCZ) zeolites, this study investigates the application of natural and pre-treated zeolites for Na+ removal from salinised groundwater. Natural BRZ achieved better Na+ removal for initial concentrations of 250-10,000 mg Na+/L and had the highest maximum adsorption capacity (14.3 ± 0.4 mg/g) compared to natural CMZ (5.8 ± 0.5 mg/g) and SCZ (5.6 ± 0.7 mg/g). Natural BRZ exhibited a higher cation exchange capacity (CEC), mineralogical purity, and natural abundance of exchangeable calcium. The natural abundance of Na+ on CMZ and SCZ may have reduced Na+ adsorption. H-form BRZ and H-form CMZ were also prepared through conventional acidic pre-treatment. Acid treatment improved zeolite properties for adsorption (surface area and CEC). Synchrotron-based X-ray scanning transmission microscopy (STXM) indicated that Na+ adsorption sites in the H-form zeolites were associated with the mineral framework. However, sorption effluents were highly acidic (pH ∼2) and Al3+ leached significantly due to the dealumination induced by acid treatment. Alternatively, hard water softening was cyclically integrated with sodium adsorption as a zeolite treatment to generate Ca/Mg-form CMZ. This integration suggested the feasibility of combining CMZ cycles for water softening and sodium reduction for an extended CMZ lifecycle. Natural CMZ was first used to treat hard water, which enriched the CMZ with Ca2+ and Mg2+ and increased its subsequent Na+ removal rate by over 77%, without producing acidic effluents. The Canadian zeolite adsorbed more sodium when water softening was integrated with sodium removal, which is a repeatable dual-treatment.

A proposed stepwise screening framework for the selection of polycyclic aromatic hydrocarbon (PAH)-degrading white rot fungi.

This study suggests a simple three-step screening protocol for the selection of white rot fungi (WRF) capable of degrading polycyclic aromatic hydrocarbons (PAHs), which combines easily applicable bioassay techniques, and verifies that protocol by evaluating the PAH degradation activity, ligninolytic enzyme secretion, and relevant gene expressions of the selected PAH-degraders. Using 120 fungal strains, a sequence of bioassay techniques was applied: Bavendamm's reaction (Step 1), remazol brilliant blue R (RBBR) decolorization (Step 2); assays for tolerance to four mixed PAHs-phenanthrene, anthracene, fluoranthene, and pyrene (Step 3). This stepwise protocol selected 14 PAH-degrading WRF, including Microporus vernicipes, Peniophora incarnata, Perenniporia subacida, Phanerochaete sordida, Phlebia acerina, and Phlebia radiata. Of these, P. incarnata exhibited the highest PAH degradative activity, ranging from 40 to > 90%, which was related to the time-variable secretions of three extracellular ligninolytic enzymes: laccase, manganese-dependent peroxidase (MnP) and lignin peroxidase (LiP). Laccase and MnP production by P. incarnata tended to be greater in the early stages of PAH degradation, whereas its LiP production became intensified with decreasing laccase and MnP production. Pilc1 and pimp1 genes encoding laccase and MnP were expressed, indicating the occurrence of extracellular enzyme-driven biodegradation of PAH by the fungal strains.

Microbial communities and biogenic Mn-oxides in an on-site biofiltration system for cold Fe-(II)- and Mn(II)-rich groundwater treatment.

This study investigated relationships between microbial communities, groundwater chemistry, and geochemical and mineralogical characteristics in field-aged biofilter media from a two-stage, pilot-scale, flow-through biofiltration unit designed to remove Fe(II) and Mn(II) from cold groundwater (8 to 15 °C). High-throughput 16S rRNA gene amplicon sequencing of influent groundwater and biofilter samples (solids, effluents, and backwash water) revealed significant differences in the groundwater, Fe filter, and Mn filter communities. These community differences reflect conditions in each filter that select for populations that biologically oxidize Fe(II) and Mn(II) in the two filters, respectively. Genera identified in both filters included relatives of known Fe(II)-oxidizing bacteria (FeOB), Mn(II)-oxidizing bacteria (MnOB), and ammonia-oxidizing bacteria (AOB). Relatives of AOB and nitrite-oxidizing bacteria were abundant in sequencing reads from both filters. Relatives of FeOB in class Betaproteobacteria dominated the Fe filter. Taxa related to Mn-oxidizing organisms were minor members of the Mn-filter communities; intriguingly, while Alphaproteobacteria dominated (40 ± 10% of sequencing reads) the Mn filter community, these Alphaproteobacteria did not classify as known MnOB. Isolates from Fe and Mn filter backwash enrichment studies provide insight on the identity of MnOB in this system. Novel putative MnOB isolates included Azospirillum sp. CDMB, Solimonas soli CDMK, and Paenibacillus sp. CDME. The isolate Hydrogenophaga strain CDMN can oxidize Mn(II) at 8 °C; this known FeOB is likely capable of Mn(II) oxidation in this system. Synchrotron-based X-ray near-edge spectroscopy (XANES) coupled with electron paramagnetic resonance (EPR) revealed the dominant Mn-oxide that formed was biogenic birnessite. Co-existence of amorphous and crystallized Mn-oxide surface morphologies on the Mn-filter media suggest occurrence of both biological and autocatalytic Mn(II) oxidation in the biofilter. This study provides evidence that biofiltration is a viable approach to remove iron, manganese, and ammonia in cold groundwater systems, and that mineralogical and microbiological approaches can be used to monitor biofiltration system efficacy and function.

Modified soil respiration model (URESP) extended to sub-zero temperatures for biostimulated petroleum hydrocarbon-contaminated sub-Arctic soils.

It has been increasingly reported that aerobic soil respiration activity (CO2 production and O2 consumption) is measurable in frozen cold-climate soils. This study modifies the Generalized Respiration (GRESP) model, a function of soil temperature (T) and unfrozen water content (M), to cover the frozen, partially frozen and unfrozen phases of successfully bioremediated, petroleum hydrocarbon-contaminated, sandy sub-Arctic soils. The Michaelis-Menten equation was modified to express the observable change in unfrozen water content near 0 °C, which is related to soil respiration activity during soil phase changes and at temperatures below the effective endpoint of detectable unfrozen water at -2 °C. The modified Michaelis-Menten equation was further combined with a Q10 temperature term, and was then incorporated into the GRESP equation to produce a new URESP model for the engineered soil bioremediation system at sub-zero temperatures. The URESP model was applied to published input data measured from the biostimulated site soils of a pilot-scale soil tank experiment conducted between -5 and 15 °C. The model fit well with the experimental data for CO2 production (R2 = 0.96) and O2 consumption (R2 = 0.92). A numerical soil thermal model (TEMP/W model) of the thawing biotreated soils in the tank was also used in this study to produce valid alternative (predictive) input T and M data for the URESP model. The URESP-derived respiration quotients (RQ; 0.695 to 0.698), or the ratios of CO2 production to O2 consumption, aligned with the experimental RQ values from the soil tank experiment (0.69) and fell within the theoretical RQ range for aerobic hydrocarbon degradation (0.63-0.80). The URESP model combined with the TEMP/W simulation approximated changes in soil respiration during thawing and characterized the computed soil respiration outputs as related to hydrocarbon utilization, based on their RQ values.

A recyclable adsorbent for salinized groundwater: Dual-adsorbent desalination and potassium-exchanged zeolite production.

This study focused on advancing the dual-adsorbent desalination technique that sequentially combines calcined layered double hydroxide (CLDH) and acid-treated zeolites (H-form zeolite) using groundwater spiked with potash mining effluent (brine). In sequential batch experiments, the CLDH adsorbent first reduced the high Cl- concentration (4600 mg/L) of saline groundwater by 96%, the Ca2+ by 90%, and the Mg2+ by 92%, while transiently raising the pH to 12.80. H-form zeolites preconditioned with Na+ then removed 92% of the Na+ (2010 mg/L), while neutralizing the adsorption effluent pH to 7.7 and lowering the sodium adsorption ratio (SAR; 139.6 to 6.6) and the hardness (574 to 48.4 mg/L). In comparison, an equivalent amount of unmodified zeolite removed only 51% of the Na+ and generated extremely hard water due to Ca2+ and Mg2+ release (1519 mg/L). Na+-conditioning the zeolites prior to acid treatment enhances native cation removal, forming H-form zeolites. Synchrotron-based X-ray scanning transmission microscopy (STXM) showed the occurrence of dealumination and visualized the sodium distribution associated with Si and Al sites in the H-form zeolites. Four consecutive desalination cycles were feasible for Na+ and K+ adsorption by regenerating the H-form zeolite. During regeneration, the Na+ desorbed while the K+ remained in the regenerated zeolites. Cumulative K+ loading in the regenerated zeolites increased from 4.8 to 21.2 mg/g, producing K-form zeolites. These K-form zeolites released K+ (2.15 mg/L for 24 h) in a leaching test and could potentially be considered as nutrient-supply media in other applications, thereby recycling the spent zeolites after multiple desalination treatments.

Enhanced bioremediation of nutrient-amended, petroleum hydrocarbon-contaminated soils over a cold-climate winter: The rate and extent of hydrocarbon biodegradation and microbial response in a pilot-scale biopile subjected to natural seasonal freeze-thaw temperatures.

A pilot-scale biopile field experiment for nutrient-amended petroleum-contaminated fine-grained soils was performed over the winter at a cold-climate site. The rate and extent of hydrocarbon biodegradation and microbial responses were determined and corresponded to the on-site soil phase changes (from unfrozen to partially frozen, deeply frozen, and thawed) associated with natural seasonal freeze-thaw conditions. Treated and untreated biopiles were constructed (~3500kg each) on an open outdoor surface at a remediation facility in Saskatoon, Canada. The treated biopile received N-P-K-based nutrient and humate amendments before seasonal freezing. Real-time field monitoring indicated significant unfrozen water content in the treated and untreated biopiles throughout the freezing period, from the middle of November to early March. Unfrozen water was slightly more available in the treated biopile due to the aqueous nutrient supply. Soil CO2 production and O2 consumption in the treated biopile were generally greater than in the untreated biopile. Total removal percentages for F2 (>C10-C16), F3 (>C16-C34), and total petroleum hydrocarbons (TPH) in the treated biopile were 57, 58, and 58%, respectively, of which 26, 39, and 33% were removed during seasonal freezing and early thawing between November to early March. F3 degradation largely occurred during freezing while F2 hydrocarbons were primarily removed during thawing. Biomarker-based hydrocarbon analyses confirmed enhanced biodegradation in the treated biopile during freezing. The soil treatment increased the first-order rate constants for F2, F3, and TPH degradation by a factor of 2 to 7 compared to the untreated biopile. Shifts in bacterial community appeared in both biopiles as the biopile soils seasonally froze and thawed. Increased alkB1 gene copy numbers in the treated biopile, especially in the partially thawed phase during early thawing, suggest extended hydrocarbon biodegradation to the seasonal freeze-thaw season, due to the nutrients supplied prior to seasonal freezing.

Synergistic desalination of potash brine-impacted groundwater using a dual adsorbent.

The impact of saline mining effluent has been a significant environmental concern. Natural and modified clay-mineral adsorbents have been receiving increasing attention for salinity reduction of brine-impacted water, especially for natural resource extraction sites and surrounding environments. In this study, a dual-adsorbent treatment based on the sequential application of calcined layered double hydroxide (CLDH) and acid-treated zeolite was developed, evaluated and characterized for the desalination of potash brine-impacted groundwater. Potash brine produced by conventional potash mining in Saskatchewan (Canada) contains a large amount of Na+, K+ and Cl-. The CLDH and acid-treated clinoptilolite zeolites were combined to sequentially remove Cl- and Na+. A series of batch adsorption experiments were conducted for synthetic saline water and potash brine-spiked groundwater using various combinations of adsorbents: natural zeolites (NZ) or acid-treated zeolites (AZ) with or without the CLDH pretreatment. The experiment revealed that the Na+ removal percentage was synergistically increased by the dechlorination pretreatment using CLDH, and further improved by AZ. The CLDH-AZ dual adsorbent achieved a Langmuir Na+ adsorption capacity of 24.4mg/g, a significant improvement over conventional approaches to zeolite-based desalination. Using the brine-impacted groundwater with a high sodium adsorption ratio (SAR) of 13.3±0.1, the CLDH-AZ dual adsorbent decreased the concentrations of Na+, K+, and Cl- by 87, 97, and 87%, respectively (below drinking water standards). It also exhibited the additional advantages of neutralizing the effluent pH and decreasing the hardness, SAR, and total dissolved sulfur concentration. This study addresses the removal mechanisms, which are associated with the structural memory effect, dealumination, protonic exchanges, and zeolite porosity changes. Synchrotron-based scanning transmission X-ray microscopy analyses provided visual evidence of sodium adsorption sites (SiONa and AlONa) associated with dealumination in the acid-treated zeolites. This study is the first report that demonstrates the synergy of the CLDH-AZ dual adsorbent treatment for potash brine-impacted water.

Biodegradation of petroleum hydrocarbons in contaminated clayey soils from a sub-arctic site: the role of aggregate size and microstructure.

This study investigates the extent of biodegradation of non-volatile petroleum hydrocarbons (C16-C34) and the associated microbial activity in predominant aggregate sizes during a pilot-scale biopile experiment conducted at 15 °C, with a clayey soil, from a crude oil-impacted site in northern Canada. The in situ aggregate microstructure was characterized by N2 adsorption and X-ray CT scanning. The soils in the nutrient (N)-amended and unamended biopile tanks were comprised of macroaggregates (>2 mm) and mesoaggregates (0.25-2 mm). Nutrient addition significantly enhanced petroleum hydrocarbon biodegradation in macroaggregates, but not in mesoaggregates. At the end of 65-d biopile experiment, 42% of the C16-C34 hydrocarbons were degraded in the nutrient-amended macroaggregates, compared to 13% in the mesoaggregates. Higher microbial activity in the macroaggregates of the nutrient amended biopile was inferred from a larger increase in extractable protein concentrations, compared to the other aggregates. Terminal Restriction Fragment Length Polymorphism (T-RFLP) of 16S rRNA genes showed that there was no selection of bacterial populations in any of the aggregates during biopile treatment, suggesting that the enhanced biodegradation in nutrient-amended macroaggregates was likely due to metabolic stimulation. X-ray micro CT scanning revealed that the number of pores wider than 4 µm, which would be easily accessible by bacteria, were an order of magnitude higher in macroaggregates. Also, N2 adsorption analyses showed that pore surface areas and pore volumes per unit weight were four to five-times larger, compared to the mesoaggregates. Thus the higher porosity microstructure in macroaggregates allowed greater hydrocarbon degradation upon biostimulation by nutrient addition and aeration.

Petroleum hydrocarbon biodegradation under seasonal freeze-thaw soil temperature regimes in contaminated soils from a sub-Arctic site.

Several studies have shown that biostimulation in ex situ systems such as landfarms and biopiles can facilitate remediation of petroleum hydrocarbon contaminated soils at sub-Arctic sites during summers when temperatures are above freezing. In this study, we examine the biodegradation of semivolatile (F2: C10-C16) and nonvolatile (F3: C16-C34) petroleum hydrocarbons and microbial respiration and population dynamics at post- and presummer temperatures ranging from -5 to 14 °C. The studies were conducted in pilot-scale tanks with soils obtained from a historically contaminated sub-Arctic site in Resolution Island (RI), Canada. In aerobic, nutrient-amended, unsaturated soils, the F2 hydrocarbons decreased by 32% during the seasonal freeze-thaw phase where soils were cooled from 2 to -5 °C at a freezing rate of -0.12 °C d(-1) and then thawed from -5 to 4 °C at a thawing rate of +0.16 °C d(-1). In the unamended (control) tank, the F2 fraction only decreased by 14% during the same period. Biodegradation of individual hydrocarbon compounds in the nutrient-amended soils was also confirmed by comparing their abundance over time to that of the conserved diesel biomarker, bicyclic sesquiterpanes (BS). During this period, microbial respiration was observed, even at subzero temperatures when unfrozen liquid water was detected during the freeze-thaw period. An increase in culturable heterotrophs and 16S rDNA copy numbers was noted during the freezing phase, and the (14)C-hexadecane mineralization in soil samples obtained from the nutrient-amended tank steadily increased. Hydrocarbon degrading bacterial populations identified as Corynebacterineae- and Alkanindiges-related strains emerged during the freezing and thawing phases, respectively, indicating there were temperature-based microbial community shifts.

Reliability of the CFTM and GPA methods for strain analysis at ultra-thin layers.

The reliability of the Computational Fourier Transform Moiré (CFTM) and Geometric Phase Analysis (GPA) techniques for strain analysis at ultra-thin layers has been investigated using computer-generated images. Our results revealed that the leakage effect creates error that is linearly dependent on the mask size used for Fourier filtering. Error due to the leakage effect has a significant impact on the analysis of strain for small-mismatched systems with low resolution in the original image. We demonstrate that the error due to the leakage effect can be minimized with improved resolution of the original image. In order to obtain a measurement of the reliability of the CFTM and GPA methods on ultra-thin layers, we systematically quantify the error due to the leakage effect as a function of image resolution and applied strain value for the original image. The presence of the leakage effect and the resulting limitations of the CFTM and GPA methods are demonstrated using a high-resolution transmission electron microscopy (HRTEM) image of an ultra-thin heterointerface from a strained layer superlattice.

Comparison of the effects of variable site temperatures and constant incubation temperatures on the biodegradation of petroleum hydrocarbons in pilot-scale experiments with field-aged contaminated soils from a cold regions site.

Temporal atmospheric temperature changes during summers at sub-Arctic sites often cause periodic fluctuations in shallow landfarm and surface soil temperatures. However, little information is available on the effect of site-relevant variations on biodegradation performance in cold climates. This study compares the rate and extents of biodegradation of petroleum hydrocarbons at variable site temperatures (1-10 °C) representative of summers at a sub-Arctic site reported previously with those obtained under a constant average temperature of 6 °C. The biodegradation was evaluated in pilot-scale landfarming experiments with field-aged petroleum-contaminated soils shipped from Resolution Island (61°30'N, 65°00'W), Nunavut, Canada. Under the variable site temperature conditions biodegradation rate constants of semi- (F2) and non-volatile (F3) hydrocarbon fractions were enhanced by over a factor of two during the 60-d experiment, compared to the constant temperature mode. The decrease in total petroleum hydrocarbons (TPH) under the variable site temperature mode was 55% compared to only 19% under the constant average temperature mode. The enhanced biodegradation is attributable to the non-linear acceleration of microbial activity between 4.7 and 10°C and faster growth of indigenous hydrocarbon-degrading microbial populations. The first-order biodegradation rate constants of 0.018, 0.024 and 0.016 d(-1) for TPH, F2 and F3 fractions at the variable site temperature were in agreement with those determined by an on-site experiment at the same site.

Biodegradation of semi- and non-volatile petroleum hydrocarbons in aged, contaminated soils from a sub-Arctic site: laboratory pilot-scale experiments at site temperatures.

This study evaluates the feasibility of landfarming biotreatment of petroleum-contaminated soils obtained from a sub-Arctic site at Resolution Island, Nunavut, Canada, and evaluates the changes in composition of the semi- and non-volatile petroleum hydrocarbon fractions during the biotreatment. Pilot-scale landfarming experiments were conducted in a laboratory in soil tanks under temperature profiles representative of the 3-year site air temperatures in July and August where temperature varied uniformly between 1 degrees C and 10 degrees C over 10 d. The site soils were acidic and N-deficient, but contained indigenous populations of hydrocarbon-degrading microorganisms. Biostimulation with nitrogen and phosphorus nutrient amendments to achieve C(TPH):N:P molar ratio of 100:9:1, and CaCO(3) amendment at 2000 mg Kg(-1) for maintaining neutral pH, and periodic 10-day tilling, reduced total petroleum hydrocarbon (TPH) concentrations by up to 64% over a 60-day period. The rate and extent of semi-volatile (F2: >C10-C16) and non-volatile (F3: >C16-C34) petroleum hydrocarbon fractions in the landfarms containing higher initial TPH levels ( approximately 2000 mg Kg(-1)) and lower TPH levels ( approximately 1000 mg Kg(-1)) were compared. Significant biodegradation of the F2 and F3 fractions occurred in both of those systems. First-order biodegradation rate constants of up to 0.019+/-0.001 d(-1) were determined for the F3 hydrocarbon fraction and were similar to the F2 fraction biodegradation rate constants of up to 0.024+/-0.005 d(-1). Biodegradation profiles of the C14, C16 and C18 alkanes revealed that at TPH concentrations above 1000 mg Kg(-1) these compounds are degraded concurrently, whereas below 1000 mg Kg(-1) the higher-molecular weight alkanes are preferentially degraded. After the 60-day treatment period, the TPH concentration was approximately 500 mg Kg(-1), and the residual TPH mass was largely associated with particles and aggregated particles with diameters of 0.6-2 mm, rather than the larger or finer particles and aggregates.