Quantification of Diclofenac in Hospital Effluent and Identification of Metabolites and Degradation Products

In this study the occurrence of diclofenac and sub‐products in effluent emerging from the University Hospital at the Federal University of Santa Maria was investigated. One metabolite was identified and, in aqueous solution, three degradation products. The quantification was conducted by means of HPLC‐DAD, and the determination of metabolite and degradation products by LC–ESI–MS/MS–QTrap. For the HPLC‐DAD method, a 70:30 mixture of methanol/sodium phosphate was used in isocratic mode. For the LC–ESI–MS/MS–QTrap determinations, a mobile phase, where phase A was an ammonium acetate solution 5 × 10^?3 mol L^?1, and phase B was methanol (5 × 10^?3 mol L^?1)/ammonium acetate (9:1, v/v), on gradient mode. The LDs for the HPLC and LC–MS/MS methods, respectively, were 2.5 and 0.02 µg L^?1, the LQs, 8.3 and 0.05 µg L^?1, and the linear range from 10 up to 2000 µg L^?1 and 0.05 up to 10 µg L^?1. As expected, the LC–ESI–MS/MS–QTrap method was more sensitive and less laborious. The metabolite 4′‐hydroxy‐diclofenac was identified. Photolysis was used for the degradation studies and three products of diclofenac were identified (m/z of 214, 286 and 303) in aqueous solution. These results notwithstanding, no degradation products of diclofenac were found in the hospital effluent.     

Determination of Sulfamethoxazole and Trimethoprim and Their Metabolites in Hospital Effluent

In this work, an analytical methodological study was carried out to determine the antimicrobials sulfamethoxazole and trimethoprim, as well as their metabolites, in hospital effluent. The determinations were conducted by liquid chromatography tandem mass spectrometry using a hybrid triple quadrupole‐linear ion trap mass spectrometer (LC‐QqLIT‐MS). The data acquisition was made in selected reaction monitoring (SRM) mode, in which two SRM transitions were monitored to ensure that the target compounds were accurately identified by the information dependent acquisition (IDA) function. The limits of detection (LOD) and quantification (LOQ) were 0.25 and 0.80 µg L^?1 for sulfamethoxazole and 0.15 and 0.50 µg L^?1 for trimethoprim. The linear range for the SMX was 0.8–100.0 µg L^?1 and TMP was 0.5–100.0 µg L^?1 on the basis of six‐point calibration curves generated by means of linear regression analysis. The coefficients of the correlation were higher than 0.999, which ensured the linearity of the method. The average concentration of sulfamethoxazole and trimethoprim found in hospital effluent was 27.8 and 6.65 µg L^?1, respectively. The analytical methodology employed allowed two metabolites to be identified, N4‐acetyl‐sulfamethoxazole and α‐hydroxy‐trimethoprim. Fragmentation pathways were proposed.     

Bioassay‐directed fractionation for analyzing estrogens in surface waters of the German Baltic Sea

A reversed‐phase fractionation method with subsequent biological and chemical analysis has been developed to estimate the contributions of the most potent estrogens to observed estrogenic effect potentials. Surface water samples were taken in the German Baltic Sea (Inner Wismar Bay and Darss Peninsula, sampling campaign July 2003) and were separated into seven individual fractions. Three fractions showed significant estrogenic activities and clear dose‐dependant responses were obtained in the yeast estrogen screen (YES). In the 2nd fractions liquid chromatographic‐electrospray‐tandem mass spectrometric (LC‐ESI‐MS‐MS) analyses showed the presence of bisphenol A (Inner Wismar Bay: 4.8 ng L^–1 and 6 ng L^–1; Darss Peninsula: 0.91 ng L^–1 and 1.7 ng L^–1) and ethinylestradiol (Inner Wismar Bay: 2.0 ng L^–1 and 6.0 ng L^–1; Darss Peninsula: < MDL and 1.7 ng L^–1), whereas estrogenic activities in the YES were only around 10% of the positive control E2. Although not identified prior in the total extract the natural hormones estradiol (Inner Wismar Bay: 0.13 ng L^–1 and 0.19 ng L^–1; Darss Peninsula: 0.12 ng L^–1 and 0.16 ng L^–1) and estriol (Inner Wismar Bay: < MDL and 0.33 ng L^–1; Darss Peninsula: < MDL) could be detected in the 3rd fractions, where high estrogenic potentials could be observed. The 4th fractions showed high responses as well and estrone were herein quantified with concentrations of 0.16 ng L^–1 and 0.18 ng L^–1 (Darss Peninsula) up to 0.37 ng L^–1 (Inner Wismar Bay). Measured and calculated estradiol equivalents for individual fractions correlated very well (R² = 0.78), when disregarding results of the 2nd fraction, where high deviations occurred.     

Occurrence of the Antimicrobials Sulfamethoxazole and Trimethoprim in Hospital Effluent and Study of Their Degradation Products after Electrocoagulation

In this study, an investigation was carried out into the occurrence of sulfamethoxazole (SMX) and trimethoprim (TMP) in the effluent of the university hospital (HUSM) of the UFSM. The degradation of these antimicrobials by the electrocoagulation (EC) process was also examined, in both the aqueous solution and hospital effluent, and a study was conducted in order to identify the subproducts formed. The experiments were optimized through factorial planning and, also, checked by response surface methodology. The best conditions for EC (achieving 58.0% of chemical oxygen demand (COD) reduction) were obtained by using 13 mA cm^?2, 500 mg L^?1 of NaCl, and 30 mm of interelectrode distance. The quantification of SMX (27.8 µg L^?1) and TMP (6.65 µg L^?1) in the hospital effluent, and the identification of the degradation products were carried out through liquid chromatography‐mass spectrometry quadrupole linear and ion trapping with electrospray ionization (LC‐ESI‐MS/MS_QTrap). Removals of 88.0% (degradation only) and 33.0% (adsorption only) were achieved for aqueous solutions of SMX and TMP, respectively, under optimized conditions. In hospital effluent samples, fortified with additions of SMX and TMP, corresponding removals of 16.0% (degradation) and 28.0% (adsorption) were achieved. This suggests that the EC process is efficient in degrading SMX in aqueous solution, although the same was not the case with TMP. The degradation products of SMX were identified (m/z 256.0 and 288.5); however, only the latter is mentioned in the literature. Toxicological aspects were not considered in this study.     

Degradation of Bezafibrate with UV/H2O2 in Surface Water and Wastewater Treatment Plant Effluent

Bezafibrate (BZF), a widely used lipid regulator, is a potential threat to ecosystems and human health in water, and the recent research showed that advanced oxidation processes (AOPs) are much more effective for BZF degradation. In this study, we investigated the photochemical decomposition of BZF in surface water and effluent from waste water treatment plants (WWTP) by UV/H₂O₂ process. The results showed that the UV/H₂O₂ process was a promising method to remove BZF at low concentration, generally at µg L^?1 level. When initial concentrations reach 100 µg L^?1 in the deionized water, >99.8% of BZF could be removed in 16 min under UV intensity of 61.4 µm cm^?2, at the H₂O₂ concentration of 0.1 mg L^?1, and neutral pH condition. Moreover, BZF degradation was inhibited in this process when humic acid (HA) and inorganic solution anions were added to the deionized water solutions, including chloride, nitrate, bicarbonate, and sulfate, significantly. In the surface water and effluent of WWTP, however, the removal efficiency of BZF was lower than that in the deionized water because of the interference of complex constituents in the surface water and effluent. Some main intermediates at the m/z range of 100–400 were observed by high performance LC‐MS (HPLC/MS) and a simple pathway of BZF degradation by UV/H₂O₂ was proposed.     

Simultaneous Analysis of Natural Free Estrogens and Their Conjugates in Wastewater by GC‐MS

A solid‐phase extraction (SPE)‐gas chromatography (GC)‐mass spectrometry (MS) analytical method was developed for the simultaneous analysis of natural free estrogens and their conjugates in wastewater samples. Natural free estrogens and their conjugates in wastewater were successfully separated by the oasis hydrophilic‐lipophilic balance solid phase extraction (Oasis HLB SPE) method, and the conjugates were initially enzyme hydrolyzed by β‐glucuronidase or arylsulfatase from Helix pomatia prior to derivatization. N‐methyl‐N‐(tert‐butyldimethylsilyl)trifluoroacetamide (MTBSTFA) plus 1% tert‐butyldimetheylchlorosilane (TBDMCS) was chosen as the derivatization reagent, and the most appropriate conditions of derivatization were determined to be at 95°C for 90 min. The recovery ratios of nine target chemicals were determined by spiking them in 1 L of ultra‐purified water or the influent of a wastewater treatment plant (WWTP). The recovery ratios of six out of nine for the analytes ranged from 73.3–114.9% with relative standard deviations (RSD) from 1.6–19.9%. The established method was successfully applied to environmental wastewater samples which were collected from one municipal wastewater treatment plant (WWTP) in Osaka, Japan, for the determination of natural free estrogens and their conjugates. In the influent sample, E1, E2, E1‐3S, E3‐3S, and E1‐3G were detected at concentrations of 16.6, 9.6, 8.2, 21.9, and 3.2 ng L^–1, respectively. However, only E1 was detected at a high concentration of 44 ng L^–1 in the effluent sample, suggesting that it is the dominant natural free estrogen in the effluent.     

Individual and Synergistic Effects of Metronidazole,Amoxicillin, and Ciprofloxacin on Methane Fermentation with Sewage Sludge

Methane fermentation is widely used to dispose of sewage sludge at wastewater treatment plants (WWTPs), due to production of renewable energy in the form of biogas. Antibiotics present in wastewater may accumulate in a sewage sludge. The aim of the present study is to investigate the impact of three antibiotics from different classes in three different doses on methane production from sewage sludge. For this purpose, metronidazole (MET), amoxicillin (AMO), and ciprofloxacin (CIP) are individually added to anaerobic reactors with sewage sludge collected from municipal WWTP. The antibiotics’ highest concentration (1024 mg kg^?1 of AMO; 512 mg kg^?1 of MET and CIP) lowers methane production and methane content in biogas. MET exerts the most marked effect and lowers methane production to 36.8 ± 3.7 mL CH₄ kg^?1 volatile solids. Tested antibiotics probably inhibit methanogenic archaea, which results in volatile fatty acids (VFAs) accumulation. Addition of MET results in accumulation of many kinds of VFAs with the highest concentration of acetic acid (17.52 ± 1.85 g L^?1). The addition of of AMO results in accumulation of butyric acid only (253.00 ± 15.89 g L^?1). However, addition of CIP results in accumulation of mainly acetic acid (7.58 ± 0.82 g L^?1) and isovaleric acid (2.01 ± 0.41 g L^?1). Next, synergistic effect of these antibiotics in a low concentration of 16 mg kg^?1 of AMO, 8 mg kg^?1 of MET, and 2 mg kg^?1 of CIP is measured in semi‐continuous conditions and causes inbibition of methane production and accumulation of VFAs.     

Toxic Cyanobacteria in Greek Freshwaters, 1987—2000: Occurrence,Toxicity, and Impacts in the Mediterranean Region

In a survey in Greece from 1987 to 2000 hepatotoxic cyanobacterial blooms were observed in 9 out of 33 freshwaters. Microcystins (MCYSTs) were detected by HPLC in 7 of these lakes, and the total MCYST concentration per scum dry weight ranged from 50.3 to 1638 ± 464 μg g^—1. Cyanobacterial genera (Microcystis, Anabaena, Anabaenopsis, Aphanizomenon, Cylindrospermopsis) with known toxin producing taxa were present in 31 freshwaters. From our data and a review of the literature, it would appear that Mediterranean countries are more likely 1) to have toxic cyanobacterial blooms consisting of Microcystis spp. and 2) to have higher intracellular MCYST concentrations. A case study in Lake Kastoria is used to highlight seasonal patterns of cyanobacterial and MCYST‐LR occurrence and to assess cyanotoxin risk. Cyanobacterial biovolume was high (> 11 μL L^—1) throughout the year and was in excess of Guidance Level 2 (10 μL L^—1) proposed by WHO for recreational waters and Alert Level 2 for drinking water. Further, surface water samples from April to November exceeded Guidance Level 3, with the potential for acute cyanobacterial poisoning. Intracellular MCYST‐LR concentrations (max 3186 μg L^—1) exceeded the WHO guideline for drinking water (1 μg L^—1) from September to November with a high risk of adverse health effects. Preliminary evidence indicates that in 3 lakes microcystins are accumulated in some aquatic organisms. Generally, a high risk level can be deduced from the data for the Mediterranean region.     

Occurrence of an Algal Mass Development in an Acidic (pH 2.5):, Iron and Aluminium‐rich Coal Mining Pond

A bloom of Chlamydomonas botryopara was observed in an extremely acid coal mining pond (pH 2.5) with high concentrations of iron and aluminium (1160...3760 mg L^–1 Fe, 133...387 mg L^–1 Al). Cell density of algae was counted as 6.45 · 10⁶ mL^–1 corresponding to 700 mg L^–1 fresh weight and 2660 μg L^–1 chlorophyll‐a. The nutrient concentrations were 3.5 mg L^–1 soluble reactive phosphorus and 0.15 mg L^–1 dissolved inorganic nitrogen. This observation supports the hypothesis that a low nutrient availability rather than extreme conditions (e.g. high acidity and low pH) limit the development of phytoplankton in many acidified lakes.     

Microcystis,Raphidiopsis raciborskii and Dolichospermum smithii,toxin producing and non-toxigenic cyanobacteria in Yezin Dam,Myanmar

Yezin Dam is a man-made reservoir located close to Yezin village in Myanmar. Its water is used for irrigation, domestic purposes and as drinking water for many urban communities in the watershed area. In recent years, increased pollution due to the concurrent development around the dam has led to water quality deterioration. No detailed study on the distribution of cyanobacteria and toxin production has been conducted so far. In order to provide insight into the extent of cyanobacteria and cyanotoxins in the dam, water samples were collected once in January 2014 for the isolation of cyanobacterial strains and eight times between March 2017 and June 2018 for the investigation of physical, chemical and biological parameters. A total of 99 phytoplankton taxa belonging to 50 genera were recorded from Yezin Dam. Microscopic examination showed that a Dolichospermum sp. was the dominant cyanobacterium followed by small numbers of Microcystis, and Raphidiopsis raciborskii in all samples throughout the sampling period. 15 isolated cyanobacterial strains were classified morphologically and phylogenetically as Dolichospermum smithii, R. raciborskii and Microcystis and tested for microcystins (MCs), cylindrospermopsins (CYNs), saxitoxins (STXs) and anatoxins (ATXs) by liquid chromatography-tandem mass spectrometry (LC–MS/MS) and enzyme-linked immunosorbent assay (ELISA). The toxin analysis of all isolated Dolichospermum strains by ELISA and LC–MS did not indicate the presence of ATXs, STXs, CYNs nor MCs. Four of the five isolated Raphidiopsis strains produced CYN and deoxyCYN. One of the isolated Microcystis strains (AB2017/08) from Yezin Dam produced 22 MC congeners. Concentrations of 0.12 μg L⁻¹ CYNs and 0.34 μg L⁻¹ MCs were also found in an environmental sample from Yezin Dam by ELISA. The potential therefore exists for the use of untreated water from Yezin Dam to cause harmful effects on humans, domestic and wild animals.     

Distribution Study of U,V, Mo,and Zr in Different Sites of Lakes Van and Hazar,River and Seawater Samples by ICP‐MS

The aim of this study is to investigate the concentrations of U, Th, V, Mo, and Zr in natural waters taken from Turkey. Among these water species, Lake Van is the largest soda lake and the fourth largest closed basin on Earth. The water samples were collected from 51 locations between 2008 and 2009. The inductively coupled plasma‐MS was used for determinations. The obtained U and Zr concentrations are in the range of 37–110 µg L^?1 and 17–78 µg L^?1 in Lake Van and 0.53–0.81 µg L^?1 and 0.15–0.19 µg L^?1 in Lake Hazar, respectively. The concentration of uranium in other studied waters varies from the lowest 0.09 µg L^?1 in Tigris (Dicle) river to the highest 4.0 µg L^?1 in Mediterranean Sea water. Mean Mo and V concentrations in the studied water samples were found to be in ranges of 0.1–17 and 2.7–113 µg L^?1, respectively. The obtained highest U concentration in Lake Van correlates with the highest Mo and Zr levels compared to the Lake Hazar and river waters. These results imply that there is a young occurrence of uranium minerals around Lake Van. It is concluded that there is about 50.000 ton of uranium in Lake Van water.     

Macrophytes’ Performance in Floating Treatment Wetlands for the Remediation of Ciprofloxacin-Contaminated Water

The presence of trace antibiotics in domestic and industrial effluents poses a risk of toxicity to fauna and flora. The application of floating treatment wetlands (FTWs) is a low-cost and sustainable approach to remediate wastewater. In this study, the performance of different macrophytes vegetated in FTWs for the remediation of ciprofloxacin (CIP)-contaminated water is investigated. Six macrophytes, Brachia mutica, Typha domingensis, Phragmites australis, Canna indica, Cyperus laevigatus, and Leptochloa fusca, are vegetated in FTWs for the removal of CIP (50 mg L⁻¹) from water. The FTWs show the potential to remove 30–43.58 mg L⁻¹ CIP from water in 28 days. They also reduce the chemical oxygen demand (118–138 mg L⁻¹) and biochemical oxygen demand (35–45 mg L⁻¹) of water. Among the macrophytes, C. indica removes maximum (43.58 mg L⁻¹) and T. domingensis minimum (30 mg L⁻¹) CIP. Canna indica and T. domingensis exhibit the maximum and minimum increase (30% and 12% of dry biomass) in growth, respectively. This study reveals that the FTWs vegetated with different plant species exhibit varying performances in removing CIP from water. This investigation is a step forward toward sustainable bioremediation of water contaminated with antibiotics.     

Cloud Point Extraction for the Preconcentration of Silver and Palladium in Real Samples and Determination by Atomic Absorption Spectrometry

A cloud point extraction procedure is presented for the preconcentration and simultaneous determination of Ag⁺ and Pd²⁺ in various samples. After complexation with 2‐((2‐((1H‐benzo[d]imidazole‐2‐yl)methoxy)phenoxy)methyl)‐1H‐benzo[d]imidazol (BIMPI), which was used as a new chelating agent, analyte ions were quantitatively extracted to a phase rich in Triton X‐114 following centrifugation, and determination was carried out by flame atomic absorption spectrometry (FAAS). Under the optimum experimental conditions (i. e., pH = 7.0, 15.0·10^–5 mol/L BIMPI and 0.036% (w/v) Triton X‐114), calibration graphs were linear in the range of 28.0–430.0 μg/L and 57.0–720.0 μg/L with detection limits of 10.0 and 25.0 μg/L for Ag⁺ and Pd²⁺, respectively. The enrichment factors were 35.0 and 28.0 for Ag⁺ and Pd²⁺, respectively. The method has been successfully applied to evaluate these metals in some real samples, including waste water, soil and hydrogenation catalyst samples.     

Selective Preconcentration of Trace Amounts of Cu(II) With Surface‐Imprinted Multiwalled Carbon Nanotubes

In this study, a new sorbent is synthesized using surface imprinting technique. Cu(II)‐imprinted multiwalled carbon nanotube sorbent (Cu(II)‐IMWCNT) is used as the solid phase in the solid‐phase extraction method. After the preconcentration procedure, Cu(II) ions are determined by high‐resolution continuum source atomic absorption spectrometry. A total of 0.1 mol L^?1 ethylenediaminetetraacetic acid (EDTA) is used to remove Cu(II) ions from the sorbent surface. The optimum experimental conditions for effective preconcentration of Cu(II), parameters such as pH, eluent type and concentration, flow rate, sample volume, sorbent capacity, and selectivity are investigated. The synthesized solid phase is characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The maximum adsorption capacities of Cu(II)‐IMWCNT and non‐imprinted solid phases are 270.3 and 14.3 mg g^?1 at pH 5, respectively. Under optimum experimental conditions for Cu(II) ions, the limit of detection is 0.07 μg L^?1 and preconcentration factor is 40. In addition, it is determined to be reusable without significant decrease in recovery values up to 100 adsorption–desorption cycles. Cu(II)‐IMWCNT have a high stability. To check the accuracy of the developed method, certified reference materials, and water samples are analyzed with satisfactory analytical results.     

Contamination of some reservoirs and lakes in Republic of Bulgaria by microcystins

This paper presents the results from analyses of water samples from 15 Bulgarian reservoirs and lakes for detection of microcystins presence by high‐performance liquid chromatography (HPLC) coupled to a ultraviolet (UV) and photo diode array (PDA) detector. In 3 of the studied drinking water reservoirs cyanobacterial blooms were not detected. Cyanobacterial blooms were observed in 6 of 12 investigated water bodies used for fishing and water sports. Microcystis was the dominant cyanobacterial genus. The concentration of total microcystins in the biomasses ranged from 8 to 1070 μg g^–1 (d.w.). Microcystin‐LR and microcystin‐RR were the predominant microcystins, followed by microcystin‐YR. Presence of dissolved microcystins was obtained in one water sample with concentration of total microcystins 1.64 μg L^–1. Presence of microcystin‐LF and ‐LW or unknown peaks possessing characteristic microcystin‐like UV‐spectra were not detected. Those first results for occurrence of microcystins in some Bulgarian reservoirs and lakes are a contribution to the knowledge on their distribution.     

Dispersive Liquid–Liquid Microextraction for Preconcentration and Determination of Nickel in Water

A method for the determination of nickel in water was developed. The procedure involves preconcentration of nickel by using dispersive liquid–liquid microextraction. The Ni(II) ions were extracted in chloroform in the form of complex with the reagent 2‐(2′‐benzothiazolylazo)‐p‐cresol. Ethanol was used as the disperser solvent. After injection of the extracting mixture in a solution of nickel, a cloudy mixture was observed. A quick centrifugation induces phase separation and thus the settling of rich phase. The nickel content in the rich phase is measured by flame atomic absorption spectrometry. Under optimal conditions, the limit of detection and quantification obtained were 1.4 and 4.7 µg L^?1, respectively. Some parameters used to characterize preconcentration systems, such as enrichment factor and consumption index were calculated and resulted in 29 and 0.34 mL, respectively. After optimization of variables and determination of analytical characteristics, the method was used for the analysis of certified reference materials (BCR‐713: wastewater, effluent and BCR‐414: plankton) and real water samples.     

Land-use dominates climate controls on nitrogen and phosphorus export from managed and natural Nordic headwater catchments

Agricultural, forestry-impacted and natural catchments are all vectors of nutrient loading in the Nordic countries. Here, we present concentrations and fluxes of total nitrogen (totN) and phosphorus (totP) from 69 Nordic headwater catchments (Denmark: 12, Finland:18, Norway:17, Sweden:22) between 2000 and 2018. Catchments span the range of Nordic climatic and environmental conditions and include natural sites and sites impacted by agricultural and forest management. Concentrations and fluxes of totN and totP were highest in agricultural catchments, intermediate in forestry-impacted and lowest in natural catchments, and were positively related %agricultural land cover and summer temperature. Summer temperature may be a proxy for terrestrial productivity, while %agricultural land cover might be a proxy for catchment nutrient inputs. A regional trend analysis showed significant declines in N concentrations and export across agricultural (−15 μg totN L⁻¹ year⁻¹) and natural (−0.4 μg NO₃-N L⁻¹ year⁻¹) catchments, but individual sites displayed few long-term trends in concentrations (totN: 22%, totP: 25%) or export (totN: 6%, totP: 9%). Forestry-impacted sites had a significant decline in totP (−0.1 μg P L⁻¹ year⁻¹). A small but significant increase in totP fluxes (+0.4 kg P km⁻² year⁻¹) from agricultural catchments was found, and countries showed contrasting patterns. Trends in annual concentrations and fluxes of totP and totN could not be explained in a straightforward way by changes in runoff or climate. Explanations for the totN decline include national mitigation measures in agriculture international policy to reduced air pollution and, possibly, large-scale increases in forest growth. Mitigation to reduce phosphorus appears to be more challenging than for nitrogen. If the green shift entails intensification of agricultural and forest production, new challenges for protection of water quality will emerge possible exacerbated by climate change. Further analysis of headwater totN and totP export should include seasonal trends, aquatic nutrient species and a focus on catchment nutrient inputs.     

Detection of Pharmaceuticals and Personal Care Products in Agricultural Soils Receiving Biosolids Application

Increasing research has suggested that biosolids generated from municipal wastewater treatment can be a major sink for many pharmaceuticals and personal care products (PPCPs) and their land application potentially introduces these contaminants into the terrestrial and aquatic environments. In this study, methods were developed for the analysis of 14 PPCPs in biosolids and soils using pressurized liquid extraction, solid phase extraction and liquid chromatography‐tandem mass spectrometry. Recoveries were over 50% for all analytes except diphenhydramine (?30%) in soils. Soil properties or type of biosolids showed minor effects on method recoveries. Estimated method limits of quantification (LOQ) range from 0.1–15 ng g^–1 for soil and 0.3–27 ng g^–1 for biosolids. A field study utilizing the methods revealed that other than carbamazepine‐10,11‐epoxide, all targeted compounds were detected in biosolids. Diphenhydramine, fluoxetine, triclosan and triclocarban were detected up to the μg g^–1 range with the highest concentration of 23 μg g^–1 for triclocarban. Seven of the PCCPs found in biosolids were also detected in agricultural soils amended with these biosolids and several (carbamazepine, diphenhydramine, and triclocarban) appeared to be persistent in soils. Triclocarban was also found most abundant in soils with the highest average concentration of 0.2 μg g^–1 while the rest of compounds were in the lower ng g^–1 range. Generally, the concentrations found on the fields were 2–3 degrees of magnitude lower than in the biosolids, which is likely to be due to dilution, degradation and leaching processes.     

Field Study of Enhanced TCE Reductive Dechlorination by a Full‐Scale Whey PRB

This study evaluates the efficiency of a full‐scale, 81 m‐wide permeable reactive barrier (PRB) configured by injection of dairy whey in the downgradient region of a contaminant source zone to enhance the in situ biodegradation of high concentrations (10² to 10³μg/L) of chlorinated ethenes (CEs). Ten biannual whey injections were completed in a 3.5‐year pilot phase and 1.5‐year operational phase. Improved and sustained dechlorination was observed at extraction/injection and downgradient wells in the fully‐operational phase, when dried whey masses were increased from 13.6 kg to 230–360 kg, whey slurry volumes were increased from 2300 L to 307,000–480,000 L, and extraction/injection well loops were employed for the application of whey. At extraction/injection wells, CEs decreased to low (≤10 μg/L) or undetectable levels. At downgradient wells, average trichloroethene concentrations decreased, by as much as 100% (from ≤384.2 during the pilot phase to ≤102.6 μg/L during the operational phase), while average cis‐dichloroethene concentrations decreased by as much as 57.5% (from ≤6466.1 to ≤4912.2 μg/L). Downgradient vinyl chloride averages either increased by as much as 63.8% (from ≤859.6 to ≤1407.9 μg/L) or decreased by 64.0% (from 1375.4 to 880 μg/L). Downgradient ethene + ethane averages increased by as much as 73.2% (from ≤1145.3 to ≤1347.1 μg/L). On the basis of the 2008 average market price, the estimated material cost of whey is $1.96/kg organic carbon or, for the configuration of an 81 m PRB by biannual application of 300 kg whey, $325/year. Carbon substrate cost comparisons and implications for efficient in situ treatment design are discussed.     

The Seashell Wastes as Biosorbent for Reactive Dye Removal from Textile Effluents

This study investigates structural and adsorption properties of the powdered waste shells of Rapana gastropod and their use as a new cheap adsorbent to remove reactive dye Brilliant Red HE‐3B from aqueous solutions under batch conditions. For the powder shells characterization, solubility tests in acidic solutions and X‐ray diffraction (XRD), scanning electron microscopy (SEM), energy‐dispersive X‐ray spectroscopy (EDX), Fourier transform IR spectroscopy (FT‐IR) and thermogravimetric analyses were performed. The results revealed that the adsorbent surface is heterogeneous consisting mainly from calcium carbonate layers (either calcite or aragonite) and a small amount of organic macromolecules (proteins and polysaccharides). The dye adsorptive potential of gastropod shells powder was evaluated as function of initial solution pH (1–5), adsorbent dose (6–40 g L^?1), dye concentration (50–300 mg L^?1), temperature (5–60°C), and contact time (0–24 h). It was observed that the maximum values of dye percentage removal were obtained at the initial pH of solution 1.2, shells dose of 40 g L^?1, dye initial concentration of 50–50 mg L^?1 and higher temperatures; the equilibrium time decreases with increasing of dye concentration. It is proved that the waste seashell powder can be used as low cost bioinorganic adsorbent for dyes removal from textile wastewaters.