Stereoselective biodegradation of amphetamine and methamphetamine in river microcosms

Here presented for the first time is the enantioselective biodegradation of amphetamine and methamphetamine in river microcosm bioreactors. The aim of this investigation was to test the hypothesis that mechanisms governing the fate of amphetamine and methamphetamine in the environment are mostly stereoselective and biological in nature. Several bioreactors were studied over the duration of 15 days (i) in both biotic and abiotic conditions, (ii) in the dark or exposed to light and (iii) in the presence or absence of suspended particulate matter. Bioreactor samples were analysed using SPE-chiral-LC-(QTOF)MS methodology. This investigation has elucidated the fundamental mechanism for degradation of amphetamine and methamphetamine as being predominantly biological in origin. Furthermore, stereoselectivity and changes in enantiomeric fraction (EF) were only observed under biotic conditions. Neither amphetamine nor methamphetamine appeared to demonstrate adsorption to suspended particulate matter. Our experiments also demonstrated that amphetamine and methamphetamine were photo-stable. Illicit drugs are present in the environment at low concentrations but due to their pseudo-persistence and non-racemic behaviour, with two enantiomers revealing significantly different potency (and potentially different toxicity towards aquatic organisms) the risk posed by illicit drugs in the environment should not be under- or over-estimated. The above results demonstrate the need for re-evaluation of the procedures utilised in environmental risk assessment, which currently do not recognise the importance of the phenomenon of chirality in pharmacologically active compounds.     

Degradation of selected pharmaceuticals in aqueous solution with UV and UV/H2O2

The degradation of four pharmaceutical compounds (PhACs), ibuprofen (IBU), diphenhydramine (DP), phenazone (PZ), and phenytoin (PHT) was investigated via ultraviolet (UV) photolysis and UV/H₂O₂ process with a low-pressure (LP) UV lamp. For each PhAC tested, direct photolysis quantum yields at 254 nm were found to be ranging from 6.32 × 10⁻² to 2.79 × 10⁻¹ mol E⁻¹ at pH 7. The second-order rate constants of the reaction between the PhACs and OH were determined to be from 4.86 × 10⁹ to 6.67 × 10⁹ M⁻¹ s⁻¹ by using a competition kinetic model which utilized para-chlorobenzoic acid (pCBA) as a reference compound. The overall effect of OH radical scavenging from humic acid (HA) and anions HCO₃⁻, NO₃⁻ was measured utilizing R_OH,UV method through examining the aqueous photodegradation of pCBA as a probe compound. Moreover, these fundamental direct and indirect photolysis parameters were applied in the model prediction for oxidation rate constants of the PhACs in UV/H₂O₂ process. It was found that the predicted oxidation rate constants approximated the observed ones. The results indicated that the new R_OH,UV probe compound method was applicable for measuring background OH radical scavenging effects in water treatment process of UV/H₂O₂. Furthermore, by GC-MS analysis, most of the intermediates created during the photodegradation of the selected PhACs in UV/H₂O₂ process were identified. For the photodegradation of PZ, a competition mechanism existed between the direct UV photolysis and the oxidation of OH. An appropriate dosage of H₂O₂ could hinder the occurrence of the direct photolysis.     

Determination of sorption of seventy-five pharmaceuticals in sewage sludge

Sorption of 75 active pharmaceutical ingredients (APIs) to three different types of sludge (primary sludge, secondary sludge with short and long sludge age respectively) were investigated. To obtain the sorption isotherms batch studies with the APIs mixture were performed in four nominal concentrations to water containing 1 g of sludge. The range of APIs concentrations was between ng L⁻¹ to μg L⁻¹ which are found in the wastewater effluents. Isotherms were obtained for approximately 45 of the APIs, providing distribution coefficients for linear (K_d), Freundlich (K_f) and Langmuir (K_L) isotherms. K_d, K_f and K_L ranging between 7.1 × 10⁴ and 3.8 × 10⁷, 1.1 × 10⁻² and 6.1 × 10⁴ and 9.2 × 10⁻³ and 1.1 L kg⁻¹, respectively. The obtained coefficients were applied to estimate the fraction of APIs in the water phase (see Abstract Graphic). For 37 of the 75 APIs, the predicted presence in the liquid phase was estimated to >80%. 24 APIs were estimated to be present in the liquid phase between 20 and 80%, and 14 APIs were found to have <20% presence in the liquid phase, i.e. high affinity towards sludge. Furthermore, the effect of pH at values 6, 7 and 8 was evaluated using one way ANOVA-test. A significant difference in K_ds due to pH changes were found for 6 of the APIs (variation 10-20%).     

Partitioning of phenanthrene into surfactant hemi-micelles on the bacterial cell surface and implications for surfactant-enhanced biodegradation

Recent studies have suggested that the ability of a surfactant to enhance the bioavailability of hydrophobic organic compounds (HOC) requires the formation of surfactant hemi-micelles on the bacterial cell surface and subsequent partitioning of HOC into the hemi-micelles. However, the studies did not provide direct evidence of HOC partitioning into surfactant hemi-micelles on the bacterial cell surface. In this study, direct evidence is provided to demonstrate that the nonionic surfactant Brij 30 forms hemi-micelles on the bacterial cell surface and that phenanthrene sorption at the bacterial surface is enhanced by the surfactant. These results are in agreement with the current theory describing surfactant-enhanced HOC bioavailability. This enhanced bioavailability is put into context with microbial kinetics and system partitioning processes, and it is demonstrated that the addition of surfactant can enhance, have no effect, or inhibit HOC biodegradation depending upon surfactant concentration and microbial growth rate. Understanding these non-linear relationships between surfactant-enhanced HOC bioavailability, biodegradation kinetics, and system partitioning will assist in the design and implementation of surfactant-enhanced bioremediation programs.     

Fate of sulfonamide antibiotics in contact with activated sludge--sorption and biodegradation

The sorption and biodegradation of three sulfonamide antibiotics, namely sulfamethoxazole (SMX), sulfadimethoxine (SDM), and sulfamonomethoxine (SMM), in an activated sludge system were investigated. Experiments were carried out by contacting 100 μg/L of each sulfonamide compound individually with 2.56 g/L of MLSS at 25 ± 0.5 °C, pH 7.0, and dissolved oxygen of 3.0 ± 0.1 mg/L in a batch reactor over different periods of 2 d and 14 d. All sulfonamides were removed completely over 11-13 d. Sorptive equilibrium was established well within the first few hours, followed by a lag period of 1-3 days before biodegradation was to deplete the antibiotic compounds linearly in the ensuing 10 days. Apparent zeroth-order rate constants were obtained by regression analysis of measured aqueous concentration vs. time profiles to a kinetic model accounting for sorption and biodegradation; they were 8.1, 7.9, and 7.7 μg/L/d for SDM, SMX, and SMM, respectively, at activated sludge concentration of 2.56 g/L. The measured kinetics implied that with typical hydraulic retention time (e.g. 6 h) provided by WWTP the removal of sulfonamide compounds from the wastewater during the activated sludge process would approximate 2 μg/L.     

Evaluation of matrices for the sorption and biodegradation of phenanthrene

Permeable reactive barriers (PRBs), a new cost effective technology for the remediation of contaminated groundwater, have rarely been considered for PAH contamination. We evaluated three candidate matrices (activated carbon (AC), pouzzolana coated (PzF) or not (Pz) with heavy fuel oil) for phenanthrene (PHE) sorption capacity and the biodegradation of adsorbed PHE. Adsorption-desorption batch experiments showed higher sorption capacity of AC than PzF (60 fold) and Pz (1,500 fold). Sorption isotherms were not linear for all matrices as described by a Freundlich model. Phenanthrene desorption from AC and PzF within 48 h was limited (1-3%). Mineralization of (14)C-PHE by a PAH-degrading bacterial strain increased in the presence of AC and Pz (+16 and +12%). Among the three matrices, AC may be a good candidate for PRBs due to high adsorption, low desorption and increased PHE degradation.     

Direct and indirect photolysis of sulfamethoxazole and trimethoprim in wastewater treatment plant effluent

The photolysis of two antibacterial compounds, sulfamethoxazole and trimethoprim, was studied in wastewater effluent. The rate of loss of sulfamethoxazole was enhanced in wastewater effluent due to indirect photolysis reactions, specifically reactions with hydroxyl radicals and triplet excited state effluent organic matter. Photolysis in the presence of natural organic matter, however, did not lead to enhanced degradation of sulfamethoxazole. Trimethoprim was also found to be susceptible to indirect photolysis in wastewater effluents, with hydroxyl radical and triplet excited effluent organic matter being the responsible species. Deoxygenation of solutions led to more rapid direct photolysis of sulfamethoxazole and trimethoprim, indicating that direct photolysis proceeds through a triplet excited state, which was verified by demonstrating that trimethoprim is a singlet oxygen sensitizer. In the wastewater effluents tested, photolysis could be apportioned into direct photolysis (48% for sulfamethoxazole, 18% for trimethoprim), reaction with hydroxyl radicals (36% and 62%, respectively) and reaction with triplet excited effluent organic matter (16% and 20%, respectively). These results indicate that allowing photolysis in wastewater stabilization ponds or wastewater treatment wetlands may lead to enhanced pharmaceutical removal prior to discharge and that effluent organic matter has different photoreactivity than natural organic matter.     

Removal of pharmaceuticals and fragrances in biological wastewater treatment

The removal of seven pharmaceuticals and two fragrances in the biological units of various full-scale municipal wastewater treatment plants was studied. The observed removal of pharmaceuticals was mainly due to biological transformation and varied from insignificant (<10%, carbamazepine) to>90% (ibuprofen). However, no quantitative relationship between structure and activity can be set up for the biological transformation. Overall, it can be concluded that for compounds showing a sorption coefficient (K(d)) of below 300 L kg(-1), sorption onto secondary sludge is not relevant and their transformation can consequently be assessed simply by comparing influent and effluent concentrations. The two fragrances (HHCB, AHTN) studied were mainly removed by sorption onto sludge. For the compounds studied, comparable transformation and sorption was seen for different reactor types (conventional activated sludge, membrane bioreactor and fixed bed reactor) as well as for sludge ages between 10 and 60-80 days and temperatures between 12 degrees C and 21 degrees C. However, some significant variations in the observed removal currently lack an explanation. The observed incoming daily load of iopromide and roxithromycin in medium-sized municipal wastewater treatment plants (up to 80,000 population equivalents) is generated by only a small number of patients: the consequences for representative 24h composite sampling are discussed. Generally, the paper presents a method for setting up mass balances for micropollutants over entire wastewater treatment plants, including an estimation of the accuracy of the quantified fate (i.e. removal by sorption and biological transformation).     

Comparison of batch sorption tests, pilot studies, and modeling for estimating GAC bed life

Saint Paul Regional Water Services (SPRWS) in Saint Paul, MN experiences annual taste and odor episodes during the warm summer months. These episodes are attributed primarily to geosmin that is produced by cyanobacteria growing in the chain of lakes used to convey and store the source water pumped from the Mississippi River. Batch experiments, pilot-scale experiments, and model simulations were performed to determine the geosmin removal performance and bed life of a granular activated carbon (GAC) filter-sorber. Using batch adsorption isotherm parameters, the estimated bed life for the GAC filter-sorber ranged from 920 to 1241 days when challenged with a constant concentration of 100 ng/L of geosmin. The estimated bed life obtained using the AdDesignS model and the actual pilot-plant loading history was 594 days. Based on the pilot-scale GAC column data, the actual bed life (>714 days) was much longer than the simulated values because bed life was extended by biological degradation of geosmin. The continuous feeding of high concentrations of geosmin (100-400 ng/L) in the pilot-scale experiments enriched for a robust geosmin-degrading culture that was sustained when the geosmin feed was turned off for 40 days. It is unclear, however, whether a geosmin-degrading culture can be established in a full-scale filter that experiences taste and odor episodes for only 1 or 2 months per year. The results of this research indicate that care must be exercised in the design and interpretation of pilot-scale experiments and model simulations for predicting taste and odor removal in full-scale GAC filter-sorbers. Adsorption and the potential for biological degradation must be considered to estimate GAC bed life for the conditions of intermittent geosmin loading typically experienced by full-scale systems.     

Occurrence of selected pharmaceuticals in an agricultural landscape, western Lake Erie basin

The occurrence of 18 commonly used pharmaceuticals was investigated in an agricultural area, which is primarily affected by runoff from agricultural fields and septic systems, on the coastline of Maumee Bay, within the western Lake Erie basin. Selected pharmaceuticals were detected in surface water, except clofibric acid and fluoxethine. The most frequently detected compounds were caffeine (88%), carbamazepine (57%) and paraxanthine (56%). Caffeine, carbamazepine, ibuprofen and paraxanthine were detected with maximum concentrations of 4.2, 1.2, 2.8 and 1.8 μg L⁻¹, respectively. However, no compound was detected in any sediment samples. In a field receiving biosolids application, pharmaceuticals were detected in the field tile drainage following biosolids application but not in soil. The occurrence of pharmaceuticals in surface water can be linked to the use of septic systems.     

Sorption and biodegradation of sulfonamide antibiotics by activated sludge: experimental assessment using batch data obtained under aerobic conditions

This study investigated the adsorption, desorption, and biodegradation characteristics of sulfonamide antibiotics in the presence of activated sludge with and without being subjected to NaN₃ biocide. Batch experiments were conducted and the relative contributions of adsorption and biodegradation to the observed removal of sulfonamide antibiotics were determined. Three sulfonamide antibiotics including sulfamethoxazole (SMX), sulfadimethoxine (SDM), and sulfamonomethoxine (SMM), which had been detected in the influent and the activated sludge of wastewater treatment plants (WWTP) in Taiwan, were selected for this study. Experimental results showed that the antibiotic compounds were removed via sorption and biodegradation by the activated sludge, though biodegradation was inhibited in the first 12 h possibly due to competitive inhibition of xenobiotic oxidation by readily biodegradable substances. The affinity of sulfonamides to sterilized sludge was in the order of SDM > SMM > SMX. The sulfonamides existed predominantly as anions at the study pH of 6.8, which resulted in a low level of adsorption to the activated sludge. The adsorption/desorption isotherms were of a linear form, as well described by the Freundlich isotherm with the n value approximating unity. The linear distribution coefficients (K_d) were determined from batch equilibrium experiments with values of 28.6 ± 1.9, 55.7 ± 2.2, and 110.0 ± 4.6 mL/g for SMX, SMM, and SDM, respectively. SMX, SMM, and SDM desorb reversibly from the activated sludge leaving behind on the solids 0.9%, 1.6%, and 5.2% of the original sorption dose of 100 μg/L. The sorbed antibiotics can be introduced into the environment if no further treatments were employed to remove them from the biomass.     

Persistence of pharmaceuticals and other organic compounds in chlorinated drinking water as a function of time

Ninety eight pharmaceuticals and other organic compounds (POOCs) that were amended to samples of chlorinated drinking-water were extracted and analyzed 1, 3, 6, 8, and 10 days after amendment to determine whether the total chlorine residual reacted with the amended POOCs in drinking water in a time frame similar to the residence time of drinking water in a water distribution system. Results indicated that if all 98 were present in the finished drinking water from a drinking-water treatment plant using free chlorine at 1.2 mg/L as the distribution system disinfectant residual, 52 POOCs would be present in the drinking water after 10 days at approximately the same concentration as in the newly finished drinking water. Concentrations of 16 POOCs would be reduced by 32% to 92%, and 22 POOCs would react completely with residual chlorine within 24 h. Thus, the presence of free chlorine residual is an effective means for transforming some POOCs during distribution.     

Sorption and degradation of selected five endocrine disrupting chemicals in aquifer material

Sorption and degradation of the five selected endocrine disrupting chemicals (EDCs) including bisphenol A (BPA), 17 beta-estradiol (E2), 17 alpha-ethynylestradiol (EE2), 4-tert-octylphenol (4-t-OP) and 4-n-nonylphenol (4-n-NP) have been investigated in the laboratory using sediment and groundwater from an aquifer in Bolivar, South Australia. The sorption coefficients measured on the sediment were in the following order: 4-n-NP>4-t-OP>EE2>E2>BPA. The sorption coefficients (Kf values) for the five EDCs were 3.89, 21.8, 24.2, 90.9 and 195, respectively. The alkylphenols 4-t-OP and 4-n-NP had strong binding on the sediment while BPA had a weak affinity. Degradation experiments of the five EDCs showed that E2 and 4-n-NP degraded quickly under aerobic conditions with a half-life of 2 and 7 days, respectively. EE2 degraded slowly with an estimated half-life of 81 days in the aquifer material under aerobic conditions while the other two chemicals (BPA and 4-t-OP) remained almost unchanged. Little or no degradation of the five EDCs except slow degradation for E2 was observed within 70 days under anaerobic conditions in native groundwater.     

Removal of selected pharmaceuticals, fragrances and endocrine disrupting compounds in a membrane bioreactor and conventional wastewater treatment plants

Eight pharmaceuticals, two polycyclic musk fragrances and nine endocrine disrupting chemicals were analysed in several waste water treatment plants (WWTPs). A membrane bioreactor in pilot scale was operated at different solid retention times (SRTs) and the results obtained are compared to conventional activated sludge plants (CASP) operated at different SRTs. The SRT is an important design parameter and its impact on achievable treatment efficiencies was evaluated. Different behaviours were observed for the different investigated compounds. Some compounds as the antiepileptic drug carbamazepine were not removed in any of the sampled treatment facilities and effluent concentrations in the range of influent concentrations were measured. Other compounds as bisphenol-A, the analgesic ibuprofen or the lipid regulator bezafibrate were nearly completely removed (removal rates >90%). The operation of WWTPs with SRTs suitable for nitrogen removal (SRT>10 days at 10 degrees C) also increases the removal potential regarding selected micropollutants. No differences in treatment efficiencies were detected between the two treatment techniques. As in conventional WWTP also the removal potential of MBRs depends on the SRT. Ultrafiltration membranes do not allow any additional detention of the investigated substances due to size exclusion. However, MBRs achieve a high SRT within a compact reactor. Nonylphenolpolyehtoxylates were removed in higher extend in very low-loaded conventional WWTPs, due to variations of redox conditions, necessary for the degradation of those compounds.     

Pathways and metabolites of microbial degradation of selected acidic pharmaceutical and their occurrence in municipal wastewater treated by a membrane bioreactor

Laboratory degradation tests with five acidic pharmaceuticals using activated sludge as inocculum under aerobic conditions were performed and microbial metabolites were analysed by liquid chromatography-mass spectrometry (LC-MS). Ketoprofen was partly mineralized as a sole source of carbon and energy and the metabolites determined by LC-MS suggest microbial ketoprofen degradation to proceed along the pathway known for biphenyls and related compounds. Bezafibrate, naproxen and ibuprofen were degraded only cometabolically whereas no transformation was obtained for diclofenac. Some biodegradation intermediates in these batch tests could be tentatively identified by means of LC-MS. The first step in microbial bezafibrate degradation appears to be the hydrolytic cleavage of the amide bond, generating well degradable 4-chlorobenzoic acid as one of the hydrolysis products. As previously found for mammals, ether cleavage and formation of desmethylnaproxen was the initial step in microbial degradation of naproxen. Two isomers of hydroxy-ibuprofen were detected as intermediates in the mineralization of ibuprofen. Laboratory studies suggest that naproxen and ibuprofen can be fully mineralized whereas more stable metabolites occur in microbial ketoprofen and bezafibrate transformation, that may deserve further attention. A LC-MS method for the trace analysis of these metabolites in water was developed and applied to municipal wastewater. Municipal wastewater treatment by a membrane bioreactor may gradually improve the removal of these pharmaceuticals.     

Fate and distribution of pharmaceuticals in wastewater and sewage sludge of the conventional activated sludge (CAS) and advanced membrane bioreactor (MBR) treatment

In this paper we report on the performances of full-scale conventional activated sludge (CAS) treatment and two pilot-scale membrane bioreactors (MBRs) in eliminating various pharmaceutically active compounds (PhACs) belonging to different therapeutic groups and with diverse physico-chemical properties. Both aqueous and solid phases were analysed for the presence of 31 pharmaceuticals included in the analytical method. The most ubiquitous contaminants in the sewage water were analgesics and anti-inflammatory drugs ibuprofen (14.6-31.3 μg/L) and acetaminophen (7.1-11.4 μg/L), antibiotic ofloxacin (0.89-31.7 μg/L), lipid regulators gemfibrozil (2.0-5.9 μg/L) and bezafibrate (1.9-29.8 μg/L), β-blocker atenolol (0.84-2.8 μg/L), hypoglycaemic agent glibenclamide (0.12-15.9 μg/L) and a diuretic hydrochlorothiazide (2.3-4.8 μg/L). Also, several pharmaceuticals such as ibuprofen, ketoprofen, diclofenac, ofloxacin and azithromycin were detected in sewage sludge at concentrations up to 741.1, 336.3, 380.7, 454.7 and 299.6 ng/g dry weight. Two pilot-scale MBRs exhibited enhanced elimination of several pharmaceutical residues poorly removed by the CAS treatment (e.g., mefenamic acid, indomethacin, diclofenac, propyphenazone, pravastatin, gemfibrozil), whereas in some cases more stable operation of one of the MBR reactors at prolonged SRT proved to be detrimental for the elimination of some compounds (e.g., β-blockers, ranitidine, famotidine, erythromycin). Moreover, the anti-epileptic drug carbamazepine and diuretic hydrochlorothiazide by-passed all three treatments investigated.Furthermore, sorption to sewage sludge in the MBRs as well as in the entire treatment line of a full-scale WWTP is discussed for the encountered analytes. Among the pharmaceuticals encountered in sewage sludge, sorption to sludge could be a relevant removal pathway only for several compounds (i.e., mefenamic acid, propranolol, and loratidine). Especially in the case of loratidine the experimentally determined sorption coefficients (K_ds) were in the range 2214-3321 L/kg (mean). The results obtained for the solid phase indicated that MBR wastewater treatment yielding higher biodegradation rate could reduce the load of pollutants in the sludge. Also, the overall output load in the aqueous and solid phase of the investigated WWTP was calculated, indicating that none of the residual pharmaceuticals initially detected in the sewage sludge were degraded during the anaerobic digestion. Out of the 26 pharmaceutical residues passing through the WWTP, 20 were ultimately detected in the treated sludge that is further applied on farmland.     

Laboratory tests on the impact of superabsorbent polymers on transformation and sorption of xenobiotics in soil taking 14C-imazalil as an example

Due to water scarcity, the agricultural production in arid areas is dependent on a sustainable irrigation management. In order to optimize irrigation systems, the application of superabsorbent polymers (SAP) as soil amendments, frequently studied within the last years, may be an appropriate measure to enhance the water holding capacity and the plant-available water in poor arable soils. These persistent polymers are also able to reduce heavy metal and salt stress to crops by accumulating those inorganic compounds. However, the impact of SAP on fate and behavior of organic xenobiotics in soil is unknown. Therefore, transformation and sorption of the model substance ¹⁴C-imazalil were monitored without and with SAP amendment in silty sand and sand soil under laboratory conditions.Within the 100-d incubation period, the transformation of ¹⁴C-imazalil was not substantially affected by the SAP amendment even though the microbial activity increased considerably. In the silty sand soil, extractable residues dropped from 90% to 45% without and from 96% to 46% with SAP amendment. Non-extractable residues continuously increased up to 49% and 35% while mineralization reached 6% and 5%, respectively. In the sand soil, characterized by its lower microbial activity and lower organic carbon content, extractable residues merely dropped from 99% to 81% and from 100% to 85% while non-extractable residues increased from 2% to 14% and 1% to 10%, respectively. Mineralization was lower than 2%. The increased microbial activity, usually promoting transformation processes of xenobiotics, was compensated by the enhanced sorption in the amended soils revealed by the increase of soil/water distribution coefficients (K_d) of 26 to 42 L kg^− 1 for the silty sand and 6 to 25 L kg^− 1 for the sand, respectively.     

Toxicity and sorption kinetics of dissolved cadmium and chromium III on tropical freshwater phytoperiphyton in laboratory mesocosm experiments

The objective of this study was to assess the interactive effects of Cd and Cr III on tropical phytoperiphyton community growth, metal sorption kinetics, as well as Cd and Cr mixtures toxicity to diatom assemblages in laboratory mesocosm experiments. A natural phytoperiphyton community sampled from the Monjolinho River (South of Brazil) was inoculated into seven experimental systems containing clean glass substrates for phytoperiphyton colonization. The communities were exposed to mixtures of dissolved Cd and Cr concentrations of 0.01 and 0.1 mg.L⁻¹ Cd and 0.05 and 0.2 mg.L⁻¹ Cr. Phytoperiphyton chlorophyll a, ash-free dry mass, growth rate, diatom cell density and diatom community composition were analyzed on samples collected after 1, 2 and 3 weeks of colonization. High Cd concentration (0.1 mg.L⁻¹) affects phytoperiphyton growth while high concentration of Cr (0.2 mg.L⁻¹) decreased the toxic effects of Cd on phytoperiphyton growth demonstrating the importance of studying metal mixtures in field studies. Shifts in species composition (development of more resistant species like Achnanthidium minutissimum (Kützing) Czarnecki, and Nitzschia palea (Kützing) Smith and reduction of sensitive ones like Fragilaria capucina Desmazières, Navicula cryptocephala (Grunow) Cleve, Encyonema silesiacum (Bleisch) Mann, Eunotia bilunaris (Ehrenberg) Mills and Gomphonema parvulum (Kützing) Kützing), of phytoperiphyton communities with increasing Cd and Cr concentrations and exposure duration have been demonstrated in this study making phytoperiphyton communities appropriate monitors of metal mixtures in aquatic systems. Good Cd and Cr accumulation capacity by phytoperiphyton was demonstrated with total and intracellular metal content in phytoperiphyton reflecting the effects of dissolved concentrations of metal in the culture media and exposure duration. Increase in both Cd and Cr reduced sequestration of each other, with generally more Cd being sequestered compared to Cr. Field validation of the observed effects remains an interesting subject for further investigations.     

Phosphorus sorption experiments and the potential for internal phosphorus loading in littoral areas of a stratified lake

The exchange of phosphorus (P) during the resuspension of sediments into shallow (oxic) waters of deep stratified lakes is regulated by equilibrium dynamics. In this study, we compared the P-sorption characteristics of sediments from 17 shallow and deep littoral sites in an oligo-mesotrophic lake. Zero Equilibrium P Concentration (EPC₀) ranged from 0.2 to 5 μg P L⁻¹. EPC₀ did not vary with sediment characteristics, but increased with increasing sediment-to-water ratios (SWR). Buffering capacity also increased with increasing SWR up to 1 g L⁻¹, at which point P concentrations were buffered almost perfectly. Therefore, internal P loading in littoral areas may depend primarily on the intensity and duration of sediment resuspension instead of sediment composition, and is expected to be spatially and temporally patchy. Maximum P-sorption capacity (S_max) varied with chemical composition of the sediments, but was generally low, indicating a limited capacity of littoral sediments to retain external inputs of P.     

Comparison of the equilibrium sorption of five organic compounds to HDPE, PP, and PVC geomembranes

This experimental investigation quantified the sorption uptake of five commonly encountered organic groundwater contaminants, methyl tertiary-butyl-ether (MTBE), benzene, trichloroethylene (TCE), 1,2-dichorobenzene (1,2-DCB), and trinitrotoluene (TNT), to geomembranes made from high density polyethylene (HDPE), polypropylene (PP), and polyvinylchloride (PVC). The organic compounds were chosen to span a range of aqueous solubilities and chemical properties. The geomembranes tested in this study exhibited sorption capacities that were of similar magnitude for each of the contaminants tested, with the exception of 1,2-DCB to HDPE, which exhibited strong uptake in comparison to the other solute/sorbent combinations. In general, the PVC geomembrane demonstrated the highest sorption capacities, while the HDPE geomembrane demonstrated the lowest sorption capacities. Measured partitioning coefficients for the contaminant/geomembrane combinations ranged from S_gf<1 to 160, but most commonly had values between 10 and 75.