N-nitrosodimethylamine (NDMA) is one of the most important disinfection by-products (DBPs) due to its carcinogenicity even at low concentrations which correspond to the levels occurring in drinking water and wastewater effluents. Therefore, NDMA is a candidate DBP that is expected to be regulated in the near future. However, the measurement of NDMA in the low nanogram per liter range is challenging because of the limitations of analytical techniques including both the sample preparation and the LC-MS/MS. Moreover, the accuracy of most of the current methods is only tested for drinking water and no information is present for other matrices. In this study, a combination of solid-phase extraction (SPE) and LC-MS/MS method that does not require high-resolution MS or advanced techniques for sample pretreatment is developed. Moreover, important factors that affect the optimization of the SPE method are provided to enable readers to optimize their own SPE procedures if necessary. The proposed method was validated for surface water, groundwater, and wastewater samples and the method quantification limit was 2 ng/L. In addition, the proposed method was used to determine the concentration of NDMA precursors measured as NDMA formation potential (NDMAFP) throughout a drinking water treatment plant at two different sampling periods. NDMAFP decreased by approximately 40 % in both samples. The concentrations ranged between 4 and 11.5 ng/L and the presence of these low concentrations underlines the need for an easy to use, yet sensitive method for the determination of NDMA in environmental matrices.

Leguminous trees have a potential for phytoremediation of oil-contaminated areas for its symbiotic association with nitrogen-fixing bacteria and arbuscular mycorrhizal fungi (AMF). This study selects leguminous tree associated with symbiotic microorganisms that have the potential to remediate petroleum-contaminated soil. Seven species of trees were tested: Acacia angustissima, Acacia auriculiformis, Acacia holosericea, Acacia mangium, Mimosa artemisiana, Mimosa caesalpiniifolia, and Samanea saman. They were inoculated with AMF mix and nitrogen-fixing bacteria mix and cultivated over five oil levels in soils, with five replicates. The decreasing of total petroleum hydrocarbons (TPH) values occurred especially with S. saman and its symbiotic microorganisms on highest oil soil contamination. Despite the large growth of A. angustissima and M. caesalpiniifolia on the highest level of oil, these species and its inoculated microorganisms did not reduce the soil TPH. Both plants were hydrocarbon tolerant but not able to remediate the polluted soil. In contrast were significative hydrocarbon decrease with M. artemisiana under high oil concentrations, but plant growth was severely affected. Results suggest that the ability of the plants to decrease the soil concentration of TPH is not directly related to its growth and adaptation to conditions of contamination, but the success of the association between plants and its symbionts that seem to play a critical role on remediation efficiency.

To provide good quality of drinking water, a biological system to remove ammonium-nitrogen (NH₄-N) from groundwater was studied in this research. The NH₄-N removal system consists of two attached growth reactors: one for nitrification and the other for hydrogenotrophic denitrification (H. denitrification). The nitrification reactor, fed by the NH₄-N contained water, could remove NH₄-N without any need of aeration. The nitrification efficiency was increased by reactor length; the highest efficiency of 92 % was achieved at the longest reactor of 100 cm. A high Fe in groundwater affected the reactor performance by decreasing the efficiency, while a low inorganic carbon (IC) had no effects. Despite of good efficiency in terms of NH₄-N removal, the nitrification reactor increased the concentration of NO₃-N in its effluent. To treat the NO₃-N, a H. denitrification reactor was set up after the nitrification reactor. Efficiency of the H. denitrification reactor was enhanced by increasing H₂ flow rates. The efficiencies were 3, 27, and 90 % for 30, 50, and 70 mL/min of H₂ flow rates, respectively. It was also found that the NO₃-N contained water (water from the nitrification reactor) had to supply IC (i.e., NaHCO₃ or CO₂) for efficient H. denitrification; however, an on-site reactor showed that it can be achieved even without IC addition. The treated water contained low NH₄-N and NO₃-N of <1.5 and <11.3 mg/L, respectively, which comply with drinking water standards. The good performance of the reactors in terms of high efficiency, no aeration need, and low H₂ supply indicated appropriateness of the system for groundwater treatment.

We examined long-term changes in soil solution chemistry associated with experimental, whole watershed-acidification at the Bear Brook Watershed in Maine (BBWM). At BBWM, the West Bear (WB) watershed has been treated with bimonthly additions of ((NH₄)₂ SO₄) since 1989. The adjacent East Bear (EB) watershed serves as a biogeochemical reference. Soil solution chemistry in the EB watershed was relatively stable from 1989–2007, with the exception of declining SO₄–S concentrations associated with a progressive decline in SO₄–S deposition during this period. Soil solution chemistry in WB reflected a progressive change in acid-neutralization mechanisms from base cation buffering to Al buffering associated with treatment during this period. Total dissolved Al concentrations progressively increased over time and were ~4× higher in 2007 than in 1989. Treatment of WB was also associated with long-term increases in soil solution H⁺, SO₄–S, and NO₃–N, whereas soil solution dissolved organic carbon (DOC) was unresponsive to treatment. For solutes such as Ca, H⁺, and SO₄–S, changes in stream chemistry were generally parallel to changes in soil solution chemistry, indicating a close coupling of terrestrial and aquatic processes that regulate the chemistry of solutions in this first-order stream watershed. For other solutes such as Al and DOC, solute concentrations were higher in soil solutions compared with streams, suggesting that sorption and transformation processes along hydrologic flow-paths were important in regulating the chemistry of solutions and the transport of these solutes.

An investigation was made to evaluate the capacity of a colorimetric artificial nose to detect toxic gas at low concentration. A low-cost and simple colorimetric sensor array for identification and quantification of NH3 with different concentrations (30, 90, 150, and 210 ppb) were reported. Using porphyrin, porphyrin derivatives (mainly metalloporphyrins), and chemically responsive dyes as the sensing elements, the developed sensor array of artificial nose showed a unique pattern of colorific change upon its exposure to NH3 with different concentrations. The dynamic responses of colorimetric sensor array to NH3 and colorimetric sensor array to various NH3 concentrations at the same time point showed that there was a positive relationship between the color change values of spots and contractions of NH3. NH3 with four concentrations were measured, and the response values at six different collection times were conducted by linear discrimination analysis (LDA) and artificial neural network (ANN). The four concentrations were discriminated completely by LDA. The response value of the colorimetric artificial nose at 0.4 min was optimum for discrimination. The method of ANN was performed and less than 5% of error by using T-S fuzzy neural network.

We determined normal plasma butyrylcholinesterase (BChE), carboxylesterase (CbE using α-NA substrate), and glutathione S-transferase (GST) activities in Caiman latirostris and Phrynops hilarii to obtain reference values for organophosphorus (OP) pesticide monitoring. BChE and CbE sensitivity to malaoxon was also evaluated. C. latirostris (N = 12; six males and six females) and P. hilarii (N = 12; seven males and five females) were obtained from the programs Yacaré (Entre Ríos Province, Argentina) and Zoo of Córdoba (Córdoba Province, Argentina). Mean total (female and male) plasma BChE activity was significantly different between reptile species, ranging between 0.337 ± 0.085 μmol min−1 ml−1 of plasma for C. latirostris and 0.251 ± 0.070 μmol min−1 ml−1 of plasma for P. hilarii. However, plasma CbE (α-NA) and GST activities were significantly higher in P. hilarii (4.81 ± 1.00 and 0.145 ± 0.045 μmol min−1 ml−1 of plasma, respectively) than in C. latirostris (0.57 ± 0.20 and 0.059 ± 0.013 μmol min−1 ml−1 of plasma, respectively). No significant differences in B-esterase and GST activities were detected between sexes, except CbE (α-NA) for C. latirostris. IC50 values for BChE and CbE (α-NA) suggested different sensitivity levels between species and between sexes. The results demonstrate that plasma esterase activity varied between species, but not between sexes (except CbE for C. latirostris). The in vitro inhibition tests indicated that CbE (α-NA) is more sensitive to inhibition than BChE. C. latirostris may be the reptile species most vulnerable to field pesticide exposure because this reptile presents the lowest CbE activity levels and its B-esterase levels seem more sensitive to OP.

A central wastewater treatment facility was built in 1997 for the town of Suwannee that eliminated 850 inadequately operating on-site sewage treatment and disposal systems. During a study in 1989–1990, Salmonella were detected in Suwannee River water samples upstream and downstream of the town of Suwannee. This study presents the findings of fecal coliform distribution between the years 1996 and 2009 in canals and the main stem of Suwannee River near the town of Suwannee, a coastal area in southeastern USA. Fecal coliforms were measured and assessed to evaluate the water quality before and after the installation of the central wastewater treatment facility. In the canals nearby the town of Suwannee, significant differences in fecal coliform concentrations were detected between the samples collected before and after the operation of the central wastewater treatment facility. Average fecal coliform of 537 most probable number (MPN)/100 ml in the canals in 1996 was reduced to 218 MPN/100 ml after the operation of wastewater treatment facility. The fecal coliform levels in canals decreased significantly in the last 13 years. Even though the average fecal coliform levels in the river was reduced from 170 to 86 MPN/100 ml before and after the installation of the wastewater treatment facility, respectively, the difference was not statistically significant.

Lead forms stable compounds with phosphate and the immobilized Pb becomes less available to soil biota. In this study, we tested the bioavailabilty of Pb using earthworms (Eisenia fetida) and plants after immobilization of Pb by a soluble P compound and an insoluble rock phosphate compound in the presence of phosphate-solubilizing bacteria (Enterobacter sp.). Rock phosphate in the presence of phosphate-solubilizing bacteria and a soluble P compound enhanced Pb immobilization as measured by NH4NO3-extractable Pb concentration, thereby reduced its bioavailability as evaluated by earthworm Pb loading and sunflower (Helianthus annuus) Pb uptake under greenhouse conditions. However, soluble P treatment increased the concentration of Pb in soil solution thereby inhibited the root elongation of mustard (Brassica hirta) seedlings. Sunflower plants in the Pb-spiked soil without P amendments showed symptoms of necrosis and stunting because of Pb toxicity. Both soluble and insoluble P treatments significantly increased shoot and root weight and decreased Pb concentration in shoot by more than 50% compared to the control. However, high Pb concentration in soil solution was found in soluble P treatment, which can be attributed to dissolved organic carbon–Pb complex formation, thereby increasing Pb mobility. The inoculation of phosphate-solubilizing bacteria can facilitate phytostabilization of Pb-contaminated site.

Clogging is the main operational problem associated with horizontal subsurface flow constructed wetlands (HSSF CWs). The measurement of saturated hydraulic conductivity has proven to be a suitable technique to assess clogging within HSSF CWs. The vertical and horizontal distribution of hydraulic conductivity was assessed in two full-scale HSSF CWs by using two different in situ permeameter methods (falling head (FH) and constant head (CH) methods). Horizontal hydraulic conductivity profiles showed that both methods are correlated by a power function (FH = CH0.7821, r 2 = 0.76) within the recorded range of hydraulic conductivities (0–70 m/day). However, the FH method provided lower values of hydraulic conductivity than the CH method (one to three times lower). Despite discrepancies between the magnitudes of reported readings, the relative distribution of clogging obtained via both methods was similar. Therefore, both methods are useful when exploring the general distribution of clogging and, specially, the assessment of clogged areas originated from preferential flow paths within full-scale HSSF CWs. Discrepancy between methods (either in magnitude and pattern) aroused from the vertical hydraulic conductivity profiles under highly clogged conditions. It is believed this can be attributed to procedural differences between the methods, such as the method of permeameter insertion (twisting versus hammering). Results from both methods suggest that clogging develops along the shortest distance between water input and output. Results also evidence that the design and maintenance of inlet distributors and outlet collectors appear to have a great influence on the pattern of clogging, and hence the asset lifetime of HSSF CWs.

The herbicide terbuthylazine is widely used within the EU; however, its frequent detection in surface and groundwater, together with its intrinsic toxicological properties, may pose a risk both for human and environmental health. Organic amendments have recently been proposed as a possible herbicide sorbent in soil, in order to limit herbicide movement from soil to water. The environmental fate of terbuthylazine depends not only in its mobility but also in its persistence. The latter is directly dependent on microbial degradation. For this reason, the effects of pine and oak residues on terbuthylazine soil microbial community functioning and on the potential of this community for terbuthylazine degradation were studied. For this purpose, degradation kinetics, soil dehydrogenase activity and the number of live bacteria were assessed in a clay loam soil treated with terbuthylazine and either amended with pine or oak wood or unamended (sterilised and non-sterilised). At day 65, 85 % of the herbicide applied still persisted in the sterile soil, 73 % in the pine-amended one and 63 % in the oak-amended and unamended ones. Pine residues increased the sorption of terbuthylazine to soil and hampered microbial degradation owing to its high terbuthylazine sorption capacity and a decrease in the bioavailability of the herbicide. On the contrary, in the presence of oak residues, the herbicide sorption did not increase significantly. The overall results confirm the active role of the soil microbial community in terbuthylazine degradation in amended and unamended soils and in a liquid enrichment culture performed using an aliquot of the same soil as the inoculum. In this clay loam soil, in the absence of amendments, the herbicide was found to be quite persistent (t ₁/₂ > 95 days), while in the enrichment culture, the same natural soil bacterial community was able to halve terbuthylazine in 24 days. The high terbuthylazine persistence in this soil was presumably ascribable to its texture and in particular to the mineralogy of the clay fraction.