PURPOSE: This study evaluates manure and chemical fertilizer effects on micronutrient (Fe, Mn, Cu, and Zn) content and availability in crops. METHODS: Seven treatments were selected, including three conventional fertilization treatments (NP, horse manure (M), and NP plus M (NPM)), three corresponding double rate fertilization (N2P2, M2, and N2P2M2), and a CK. Soil samples were collected and separated into four aggregates by wet-sieving in September 2009. Corn samples were collected and analyzed simultaneously. RESULTS: Treatment N2P2 increased DTPA extractable Fe, Mn, and Cu in soil by 732%, 388%, and 42%, whereas M2 decreased the corresponding values by 26%, 22%, and 10%, respectively, compared to CK. DTPA extractable Zn in soil and Zn in corn grain were higher in the M and M2 treatments than in the other treatments, and DTPA Zn was significantly correlated with soil organic carbon (SOC) in large macroaggregate, microaggregate, and silt + clay fractions. The Mn concentrations in corn stalks and grain were significantly correlated with DTPA extractable Mn in bulk soil and microaggregates, and Zn in stalks were significantly correlated with DTPA Zn in bulk soil, microaggregates, and large macroaggregates. CONCLUSIONS: Long-term application of horse manure could increase soil Zn availability and uptake by corn, possibly due to its activation by SOC. In contrast, chemical fertilizer application increased DTPA extractable Fe, Mn, and Cu in soil by reducing soil pH. Our results also suggest that Mn uptake by corn originated mainly in microaggregates, whereas Zn in crops was primarily sourced from large macroaggregates and microaggregates.

PURPOSE: The present research aims to investigate the individual and interactive effects of chlorine dose/dissolved organic carbon ratio, pH, temperature, bromide concentration, and reaction time on trihalomethanes (THMs) formation in surface water (a drinking water source) during disinfection by chlorination in a prototype laboratory-scale simulation and to develop a model for the prediction and optimization of THMs levels in chlorinated water for their effective control. METHODS: A five-factor Box–Behnken experimental design combined with response surface and optimization modeling was used for predicting the THMs levels in chlorinated water. The adequacy of the selected model and statistical significance of the regression coefficients, independent variables, and their interactions were tested by the analysis of variance and t test statistics. RESULTS: The THMs levels predicted by the model were very close to the experimental values (R 2 = 0.95). Optimization modeling predicted maximum (192 μg/l) TMHs formation (highest risk) level in water during chlorination was very close to the experimental value (186.8 ± 1.72 μg/l) determined in laboratory experiments. The pH of water followed by reaction time and temperature were the most significant factors that affect the THMs formation during chlorination. CONCLUSION: The developed model can be used to determine the optimum characteristics of raw water and chlorination conditions for maintaining the THMs levels within the safe limit.

INTRODUCTION: We conducted a yearly polluted-reference sampling to assess the effects of petroleum pollution on life cycle characteristics of the meiobenthic nematode Odontophora villoti. Samples were taken every 15 days between 26 November 2004 and 25 November 2005 from two beaches of Bizerte bay (Tunisia), Rimel and Tunisian Refining Industries Company (TRIC). The latter site is located in front of the “Tunisian Refining Industries Company” runoff. DISCUSSION: When compared to the reference site, the mean body dimensions of O. villoti from the impacted site were significantly lower. The small size of affected nematodes was represented both by the length and width as a function of the life stage. It was also established that changes in lengths of body parts during molts were different between the two study sites. The low availability of oxygen from April to August seems to prevent the formation of embryos of O. villoti. Thus, two annual reproductive cycles with different durations were observed in Rimel and TRIC. Under stress, juvenile phase and egg production were generally shorter. Globally, the impact of petroleum pollution on O. villoti was expressed by a short egg-to-egg development time. CONCLUSION: Our study assessed the usefulness of life cycle characteristics (biometry and life stage durations) of O. villoti in biomonitoring, and the results are generally consistent suggesting that this species may be considered as an efficient bioindicator.

PURPOSE: The present research aims to optimize the removal of ibuprofen (IBP), a non-steroidal anti-inflammatory, analgesic, and antipyretic drug from the aqueous solution using a synthesized magnetic carbon–iron nanocomposite, and to investigate the individual and combined effects of the independent process variables. METHOD: Combining the adsorptive capability of carbon and magnetic property of iron, a carbon–iron nanocomposite was synthesized. A four-factor Box–Behnken experimental design-based optimization modeling was performed for maximizing the removal of IBP from water by the nanocomposite using the batch experimental data. A quadratic model was built to predict the responses. Significance of the process variables and their interactions was tested by the analysis of variance and t test statistics. RESULTS: The experimental maximum removals of IBP from the aqueous solution by carbon and magnetic nanocomposite were 14.74% and 60.39%, respectively. The model predicted maximum removal of 65.81% under the optimum conditions of the independent variables (IBP concentration 80 mg/l; temperature 48°C; pH 2.50; dose 0.6 g/l) was very close to the experimental value (65.12 ± 0.92%). pH of the solution exhibited most significant effect on IBP adsorption. CONCLUSION: The developed magnetic nanocomposite was found superior than its precursor carbon exhibiting higher removal of IBP from the water and can be easily separated from the aqueous phase under temporary external magnetic field. The developed magnetic nanocomposite may be used for an efficient removal of IBP from the water.

INTRODUCTION: The aims of the present study are to investigate the effects of Ce3+ on the growth and some antioxidant metabolisms in rice seedlings (Oryza sativa L. cv Shengdao 16). MATERIALS AND METHODS: The rice was treated with 0, 0.05, 0.1, 0.5, 1.0, and 1.5 mM Ce3+, respectively. The growth index of rice was measured. The chlorophyll content; catalase, superoxide dismutase, and peroxidase activities; and the level of hydrogen peroxide (H2O2), superoxide anion (O 2 ·− ), and malondialdehyde were assayed. The accumulation of Ce3+ and the uptake of mineral nutrition elements were analyzed with ICP-SF-MS. RESULTS AND DISCUSSION: Hormetic effects of Ce3+ on the growth and some antioxidant metabolisms were found in the roots and shoots of rice. The roots can accumulate a much higher content of Ce3+ than shoots and Ce3+ mainly located in the cell wall of roots. Moreover, the uptake of K, Mg, Ca, Na, Fe, Mn, Zn, Cu, and Mo in the roots and shoots was affected with the exposure of different Ce3+ treatments, which indicated that Ce3+ affected the nutritional status of roots and shoots and further affected the growth of rice. CONCLUSION: The appropriate amount of Ce3+ improved the defense system and growth of rice. The roots can accumulate a much higher content of Ce3+ than shoots. Moreover, the uptake of K, Mg, Ca, Na, Fe, Mn, Zn, Cu, and Mo in the roots and shoots was affected with the exposure of different Ce3+ treatments.

PURPOSE: This study aimed to investigate the removal mechanisms of pharmaceutical active compounds (PhACs) and musks in a wastewater treatment plant (WWTP). Biological removal and adsorption in the activated sludge tank as well as the effect of UV radiation used for disinfection purposes were considered when performing a mass balance on the WWTP throughout a 2-week sampling campaign. METHODS: Solid-phase extraction (SPE) was carried out to analyse the PhACs in the influent and effluent samples. Ultrasonic solvent extraction was used before SPE for PhACs analysis in sludge samples. PhAC extracts were analysed by LC-MS. Solid-phase microextraction of liquid and sludge samples was used for the analysis of musks, which were detected by GC-MS. The fluxes of the most abundant compounds (13 PhACs and 5 musks) out of 79 compounds studied were used to perform the mass balance on the WWTP. RESULTS: Results show that incomplete removal of diclofenac, the compound that was found in the highest abundance, was observed via biodegradation and adsorption, and that UV photolysis was the main removal mechanism for this compound. The effect of adsorption to the secondary sludge was often negligible for the PhACs, with the exceptions of diclofenac, etofenamate, hydroxyzine and indapamide. However, the musks showed a high level of adsorption to the sludge. UV radiation had an important role in reducing the concentration of some of the target compounds (e.g. diclofenac, ibuprofen, clorazepate, indapamide, enalapril and atenolol) not removed in the activated sludge tank. CONCLUSIONS: The main removal mechanism of PhACs and musks studied in the WWTP was most often biological (45%), followed by adsorption (33%) and by UV radiation (22%). In the majority of the cases, the WWTP achieved >75% removal of the most detected PhACs and musks, with the exception of diclofenac.

PURPOSE: Dechlorination of polychlorinated biphenyls (PCBs) by nanoscale zerovalent iron (NZVI) is often strongly hindered by increased pH because large amounts of H+ ions were consumed during the surface reaction. The main objective of this work was to evaluate the effect of pH control in acid on the dechlorination processes of PCBs and to compare the dechlorination efficiency between 2,4,4′-trichlorobiphenyl (2,4,4′-CB) and the extracted PCBs from the field PCBs-contaminated soil in this system. METHODS: The reaction solution pH was controlled to be weakly acid (4.90–5.10) with an automatic pH control system, in which the dechlorination of 2,4,4′-CB and extracted PCBs from a PCBs-contaminated soil by NZVI and palladized nanoscale zerovalent iron (NZVI/Pd) was investigated. RESULTS: To control the reaction solution pH to be acid actually increased the dechlorination rate of PCBs by NZVI and NZVI/Pd. The observed normalized pseudo-first-order dechlorination rate constants (k obs) of 2,4,4′-CB increased from 0.0029 min−1 (no pH control) to 0.0078 min−1 (pH control) by NZVI and from 0.0087 min−1 (no pH control) to 0.0108 min−1 (pH control) by NZVI/Pd. In the case of NZVI/Pd, the chlorines in the para position were much more easily dechlorinated than ortho position, and biphenyl was the dominating product. As the solution pH was controlled at 4.90–5.10, the dechlorination rate constants of PCB congeners extracted from soil (k obs) were 0.0027–0.0033 min−1 and 0.0080–0.0098 min−1 by NZVI and NZVI/Pd, respectively. CONCLUSIONS: To keep the reaction solution to be weakly acid markedly increased the dechlorination rate of PCBs, which may offer a novel technology in the remediation of PCBs-contaminated soil.

PURPOSE: The presence of four phenolic endocrine disrupting compounds (EDCs: nonylphenol [NP], NP monoethoxylate[NP1EO], bisphenol A [BPA], triclosan, [TCS]) and four nonsteroidal anti-inflammatory drugs (NSAIDs: ibuprofen[IBF], ketoprofen [KFN], naproxen [NPX], diclofenac [DCF]) in a Greek river receiving treated municipal wastewater was investigated in this study. METHODS: Samples were taken from four different points of the river and from the outlet of a sewage treatment plant (STP) during six sampling campaigns, and they were analyzed using gas chromatography–mass spectrometry. RESULTS: According to the results, EDCs were detected in almost all samples, whereas NSAIDs were detected mainly in wastewater and in the part of the river that receives wastewater from the STP. Among the target compounds, the highest mean concentrations in the river were detected for NP (1,345 ng L−1) and DCF (432 ng L−1). Calculation of daily loads of the target compounds showed that STP seems to be the major source of NSAIDs to the river, whereas other sources contribute significantly to the occurrence of EDCs. The environmental risk due to the presence of target compounds in river water was estimated, calculating risk quotients for different aquatic organisms (algae, daphnids, and fish). Results denoted the possible threat for the aquatic environment due to the presence of NP and TCS in the river.

INTRODUCTION: Microcystins (MCs; cyclic heptapeptides) are produced by freshwater cyanobacteria and cause public health concern in potable water supplies. There are more than 60 types of MCs identified to date, of which MC-LR is the most common found worldwide. For MC-LR, the WHO has established a threshold value of 1 μg L−1 for drinking water. The present MCs removal methods such as coagulation, flocculation, adsorption, and filtration showed low efficiency for removing dissolved MC fraction from surface waters to the stipulated limit prescribed by WHO based on MC health impacts. The search for cost-effective and efficient removal method is still warranted for remediation of dissolved MC-LR-contaminated water resources. MATERIALS AND METHODS: Molecularly imprinted polymer (MIP) adsorbent has been prepared using non-covalent imprinting approach. Using MC-LR as a template, itaconic acid as a functional monomer, and ethylene glycol dimethacrylate as a cross-linking monomer, a MIP has been synthesized. Computer simulations were used to design effective binding sites for MC-LR binding in aqueous solutions. Batch binding adsorption assay was followed to determine binding capacity of MIP under the influence of environmental parameters such as total dissolved solids and pH. RESULTS AND DISCUSSION: The adsorptive removal of MC-LR from lake water has been investigated using MIPs. The MIP showed excellent adsorption potential toward MC-LR in aqueous solutions with a binding capacity of 3.64 μg mg−1 which is about 60% and 70% more than the commercially used powdered activated carbon (PAC) and resin XAD, respectively. Environmental parameters such as total organic carbon (represented as chemical oxygen demand (COD)) and total dissolved solids (TDS) showed no significant interference up to 300 mg L−1 for MC-LR removal from lake water samples. It was found that the binding sites on PAC and XAD have more affinity toward COD and TDS than the MC-LR. Further, the adsorption capacity of the MIP was evaluated rigorously by its repeated contact with fresh lake water, and it was found that the adsorption capacity of the MIP did not change even after seven adsorption/desorption cycles. The contaminated water of MC-LR (1.0 μg L−1) of 3,640 L could be treated by 1 g of MIP with an estimated cost of US $1.5. CONCLUSIONS: The adsorption capacity of the MIP is 40% more than commercially used PAC and resins and also the polymer showed reusable potential which is one of the important criteria in selection of cyanotoxins remediation methods.