The impact of station location on water quality characterization in the Loxahatchee National Wildlife Refuge

Water quality was monitored in the Loxahatchee National Wildlife Refuge based on the Consent Decree (CDN), the Enhanced Refuge (ERN), the four-part Test impacted (FPTIN), and the four-part test unimpacted (FPTUN) networks. Alkalinity, dissolved organic carbon, total organic carbon, dissolved oxygen, total dissolved solids, total suspended solids, turbidity, pH, specific conductivity, calcium, chloride, silicon, sulfate, and total phosphorus (TP) were measured from 2005 through 2009. When the ERN was used, the 10 μg TP L^?1 Consent Decree limit would have been exceeded and would have ranged from a low of 2 months in 2009 to a high of 9 months in 2005. Based on the CDN, the limit exceeded only for 1 month in each year from 2006 through 2008. Based on the FPTIN, the 10 μg TP L^?1 limit would have been exceeded and would have ranged from a low of 1 month in 2007 to a high of 7 months in 2005 and 2008. Based on the CDN, the limit only exceeded for 1 month in each year from 2006 through 2008. Since TP is rapidly removed from canal water intruded into the Refuge marsh, one cannot expect a water quality sampling station located 2 km from the source to reliably detect violations. This may be the primary reason why there have been very few months when TP concentration has exceeded the limit since 1992 or part four of the four-part test annual 15 μg?L^?1 limit since 2006.     

A method developed for determination of heptachlor and its metabolites from pork

A new method has been developed to determine heptachlor and its metabolites heptachlor-exo-epoxide and heptachlor-endo-epoxide in pork. The pork samples were extracted with acetone–n-hexane (2:8, V:V) and cleaned up by gel permeation chromatography and florisil solid-phase extraction cartridge. The extract was then determined by gas chromatography equipped with electron capture detector (GC-ECD), followed by validation using gas chromatography–mass spectrometry (GC–MS) with negative chemical ionization. Linearity of calibration curves ranged from 0.01 to 0.5 mg L^?1, with correlation coefficients of more than 0.9980 for GC-ECD and GC–MS, respectively. At spiked concentrations of 0.01, 0.05, and 0.1 mg kg^?1, the average recovery and relative standard deviation values were 87.1–102.2 and 4.0–11.3 %, respectively. The limit of quantification for each analyte was 0.01 mg kg^?1, which satisfied the current maximum residue limit permitted in pork. Our results showed that the method developed was successfully used to determine heptachlor and heptachlor epoxide residues in real pork samples.     

Rapid spectrophotometric determination of trace amounts of palladium in water samples after dispersive liquid–liquid microextraction

A simple, rapid, and efficient dispersive liquid–liquid microextraction method, followed by UV–Vis spectrophotometry was developed for the preconcentration and determination of Pd ions in water samples. Pd ions react with α-furildioxime (chelating agent) to form a hydrophobic complex. Various parameters were altered to study and optimize their effects on the extraction efficiency, such as pH, ligand concentration, the type and volume of extraction and dispersive solvents, extraction time, and salt concentration. Under optimized conditions, the method exhibited an enrichment factor (C _org/C _aq) of 25 and recovery more than 98 % within a very short extraction time. The linearity of the method ranged from 10 to 200 μg?L^?1. The limit of detection was 1.1 μg?L^?1. The relative standard deviation for the concentration of 100 μg?L^?1 of Pd was 2.3 % (n?=?10). Finally, the developed method was successfully applied to the extraction and determination of Pd in tap, river, mineral, and sea water samples.     

Solid phase extraction and determination of Cr(III) by spectrophotometry using cefaclor as a complexing reagent and FAAS

The present study reports on the application of modified groundnut shell as a new, easily prepared, and stable sorbent for the extraction of trace amount of Cr(III) in aqueous solution. 2-Hydroxybenzaldiminoglycine was immobilized on groundnut shells in alkaline medium and then used as a solid phase for the column preconcentration of Cr(III). The elution was carried out with 3 mL of 2 mol?L^?1 HCl. The amount of eluted Cr(III) was determined by spectrophotometry using cefaclor as a complexing reagent and by flame atomic absorption spectrometry (FAAS). Different experimental variables such as pH, amount of solid sorbent, volume and concentration of eluent, sample and eluent flow rate, and interference of other metal ions on the retention of Cr(III) were studied. Under the optimized conditions, the calibration curves were found to be linear over the concentration range of 13–104 and 10–75 μg?L^?1 with a detection limit of 3.64 and 1.24 μg?L^?1 for spectrophotometric method and FAAS, respectively. An enrichment factor of 200 and RSD of ±1.19–1.49 % for five successive determinations of 25 μg?L^?1 were achieved. The column preconcentration was successfully applied to the analysis of tap water and underground water samples.     

Application of zirconium–iridium permanent modifier for the simultaneous determination of lead, cadmium, arsenic, and nickel in atmospheric particulate matter by multi-element electrothermal atomic absorption spectrometry

A novel and robust method for the simultaneous determination of lead, cadmium, arsenic, and nickel in atmospheric particulate matter by multi-element electrothermal atomic absorption spectrometry was developed, using zirconium–iridium coating as permanent modifier (140 μg Zr and 4 μg Ir). After 300 atomization cycles, it was necessary to add 2 μg of Ir. Due to the varying concentrations of Pb in atmospheric particulate matter, lead was monitored at two wavelengths, at the less sensitive line of 261.4 nm for high concentration samples (>20 μg?L^?1) or at 283.3 nm for the low concentration samples. Matrix-matched calibration had to be performed for quantitative recoveries (96–102 %). Following this approach, the four elements were determined in atmospheric particulate matter samples from an industrial area near the city of Athens in two different time periods (cold–warm) with limits of detection of 5.5 ng?m^?3 for Pb at 261.4 nm and 0.29 ng?m^?3 at 283.3 nm, 0.019 ng?m^?3 for Cd, 0.14 ng?m^?3 for As, and 0.22 ng?m^?3 for Ni. Lead, Cd, and As levels were very low, whereas Ni content was at comparable levels with other areas worldwide.     

A nanosilver-based spectrophotometric method for determination of malachite green in surface water samples

A new spectrophotometric method is reported for the determination of nanomolar level of malachite green in surface water samples. The method is based on the catalytic effect of silver nanoparticles on the oxidation of malachite green by hexacyanoferrate (III) in acetate–acetic acid medium. The absorbance is measured at 610 nm with the fixed-time method. Under the optimum conditions, the linear range was 8.0?×?10^?9–2.0?×?10^?7?mol?L^?1 malachite green with a correlation coefficient of 0.996. The limit of detection (S/N?=?3) was 2.0?×?10^?9?mol?L^?1. Relative standard deviation for ten replicate determinations of 1.0?×?10^?8?mol?L^?1 malachite green was 1.86 %. The method is featured with good accuracy and reproducibility for malachite green determination in surface water samples without any pre-concentration and separation step.     

Groundwater phosphorus in forage-based landscape with cow-calf operation

Forage-based cow-calf operations may have detrimental impacts on the chemical status of groundwater and streams and consequently on the ecological and environmental status of surrounding ecosystems. Assessing and controlling phosphorus (P) inputs are, thus, considered the key to reducing eutrophication and managing ecological integrity. In this paper, we monitored and evaluated P concentrations of groundwater (GW) compared to the concentration of surface water (SW) P in forage-based landscape with managed cow-calf operations for 3 years (2007–2009). Groundwater samples were collected from three landscape locations along the slope gradient (GW1 10–30 % slope, GW2 5–10 % slope, and GW3 0–5 % slope). Surface water samples were collected from the seepage area (SW 0 % slope) located at the bottom of the landscape. Of the total P collected (averaged across year) in the landscape, 62.64 % was observed from the seepage area or SW compared with 37.36 % from GW (GW1?=?8.01 %; GW2?=?10.92 %; GW3?=?18.43 %). Phosphorus in GW ranged from 0.02 to 0.20 mg L^?1 while P concentration in SW ranged from 0.25 to 0.71 mg L^?1. The 3-year average of P in GW of 0.09 mg L^?1 was lower than the recommended goal or the Florida’s numeric nutrients standards (NNS) of 0.12 mg P L^?1. The 3-year average of P concentration in SW of 0.45 mg L^?1 was about fourfold higher than the Florida’s NNS value. Results suggest that cow-calf operation in pasture-based landscape would contribute more P to SW than in the GW. The risk of GW contamination by P from animal agriculture production system is limited, while the solid forms of P subject to loss via soil erosion could be the major water quality risk from P.     

Groundwater quality assessment in the urban-west region of Zanzibar Island

This paper highlights the levels of anions (nitrate, nitrite, sulfate, bromide, chloride, and fluoride) and cations (potassium, sodium, magnesium, and calcium) in selected springs and groundwater sources in the urban-west region of Zanzibar Island. The levels of total dissolved solids (TDS) and sodium adsorption ratio (SAR) were also studied. Thirty water samples were collected in December 2012 from various types of water sources, which included closed hand-dug wells (CHDW), open hand-dug wells (OHDW), springwater (SW), public bore wells (PBW), and bore wells owned by private individuals (BWP), and analyzed after filtration and sometimes dilution. The cations were analyzed using inductively coupled plasma-optical emission spectrometry (ICP-OES). The anions were analyzed by chemically suppressed ion chromatography (IC). The ranges of the levels of the investigated parameters were as follows: Na 13.68–3,656 mg L^?1, K 2.66–583 mg L^?1, Mg 0.63–131.10 mg L^?1, Ca 16.79–189.9 mg L^?1, Cl^? 8.61–4,340.97 mg L^?1, F^? 0–1.02 mg L^?1, Br^? 0–10.88 mg L^?1, NO₃ ^? 0.18–342.4 mg L^?1, NO₂ ^? 0–1.39, SO₄ ^2? 4.43–534.02 mg L^?1, TDS 7–6,380 mg L^?1, and SAR 0.63–50. Except fluoride, most of the studied parameters in the water samples had concentrations beyond the permissible limits of the World Health Organization (WHO). The elevated concentrations are a result of seepage of contaminated water from on-site septic tanks, pit latrines, landfill leachates, fertilizer applications, and domestic effluents. These results should alert domestic water stakeholders in Zanzibar to the urgent task of initiating a quick mitigation response to control these alarming water risks.     

Occurrence of haloacetic acids (HAAs) and trihalomethanes (THMs) in drinking water of Taiwan

In this study, water samples were collected from 86 water treatment plants for analysis of haloacetic acids (HAAs) and trihalomethanes (THMs) from February to March, 2007 and from July to August, 2007. Both seasonal and geographical variations of disinfection by-products (DBPs) in drinking water of Taiwan were presented. The results showed that the five HAA concentrations (HAA5) were 1.0–38.9 μg/L in the winter and 0.2–46.7 μg/L in the summer; and the total THMs were ND-99.4 μg/L in the winter and ND-133.2 μg/L in the summer. For samples taken from the main Taiwan island, dichloroacetic acid (29.4–31.7%) and trichloroacetic acid (25.3–27.6%) were the two major HAA species, and trichloromethane was the major THM species (49.9–62.2%) in finished water. For water treatment plants located on the offshore islands outside of Taiwan, high bromide concentration was found in raw water, and higher percentage of brominated THMs and HAAs were formed in the overall formation. A statistically significant (P?<?0.005) logarithmic linear regression model was found to be useful to describe the correlations between TTHM and HAA5 or nine HAAs (HAA5?=?1.219 ×TTHM ^0.754, R ²?=?0.658; HAA9?=?1.824 ×TTHM ^0.735, R ²?=?0.678). No apparent difference was observed for DBPs concentrations between finished water and distribution samples in this study.     

Quantification of penoxsulam in soil and rice samples by matrix solid phase extraction and liquid-liquid extraction followed by HPLC-UV method

The paper exploits the development of novel, simple and sensitive methodology involving matrix solid phase dispersion (MSPD) and the comparison of MSPD with liquid-liquid extraction (LLE) for the evaluation of residual penoxsulam in soil and rice samples. Extracted samples were analyzed by high-performance liquid chromatography (HPLC) with ultraviolet detector at 230 nm. Both methods were optimized, considering different parameters, and under optimum conditions, the mean recoveries obtained were in the range of 85–104 % for MSPD and 78.8–90.7 % for LLE. Precision values expressed as relative standard deviation (RSD) were ≤10 for MSPD and ≤15 for LLE. Linearity for penoxsulam was in the range of 0.01–20 μg mL^?1 with limits of detection and limits of quantification of 0.01 and 0.03 mg kg^?1, respectively.     

Assessment of the labile fractions of copper and zinc in marinas and port areas in Southern Brazil

The dissolved labile and labile particulate fractions (LPF) of Cu and Zn were analyzed during different seasons and salinity conditions in estuarine waters of marina, port, and shipyard areas in the southern region of the Patos Lagoon (RS, Brazil). The dissolved labile concentration was determined using the diffusive gradients in thin films technique (DGT). DGT devices were deployed in seven locations of the estuary for 72 h and the physicochemical parameters were also measured. The LPF of Cu and Zn was determined by daily filtering of water samples. Seasonal variation of DGT–Cu concentrations was only significant (p?<?0.05) at one shipyard area, while DGT–Zn was significant (p?<?0.05) in every locations. The LPF of Cu and Zn concentrations demonstrated seasonal and spatial variability in all locations, mainly at shipyard areas during high salinity conditions. In general, except the control location, the sampling locations showed mean variations of 0.11–0.45 μg?L^?1 for DGT–Cu, 0.89–9.96 μg?L^?1 for DGT–Zn, 0.65–3.69 μg?g^?1 for LPF–Cu, and 1.35–10.87 μg?g^?1 for LPF–Zn. Shipyard areas demonstrated the most expressive values of labile Cu and Zn in both fractions. Strong relationship between DGT–Zn and LPF–Zn was found suggesting that the DGT–Zn fraction originates from the suspended particulate matter. Water salinity and suspended particulate matter content indicated their importance for the control of the labile concentrations of Cu and Zn in the water column. These parameters must be taken into consideration for comparison among labile metals in estuaries.     

The use of a natural coagulant (Opuntia ficus-indica) in the removal for organic materials of textile effluents

The goal of this study was to investigate the activity of the coagulant extracted from the cactus Opuntia ficus-indica (OFI) in the process of coagulation/flocculation of textile effluents. Preliminary tests of a kaolinite suspension achieved maximum turbidity removal of 95 % using an NaCl extraction solution. Optimization assays were conducted with actual effluents using the response surface methodology (RSM) based on the Box–Behnken experimental design. The responses of the variables FeCl₃, dosage, cactus dosage, and pH in the removal of COD and turbidity from both effluents were investigated. The optimum conditions determined for jeans washing laundry effluent were the following: FeCl₃ 160 mg L^?1, cactus dosage 2.60 mg L^?1, and pH 5.0. For the fabric dyeing effluent, the optimum conditions were the following: FeCl₃ 640 mg L^?1, cactus dosage 160 mg L^?1, and pH 6.0. Investigation of the effects of the storage time and temperature of the cactus O. ficus-indica showed that coagulation efficiency was not significantly affected for storage at room temperature for up to 4 days.     

Assessment of cylindrospermopsin toxin in an arid Saudi lake containing dense cyanobacterial bloom

This study reports the presence of the cyanobacterial toxin cylindrospermopisn (CYN) and its producer Cylindrospermopsis raciborskii for the first time in Saudi freshwater sources. C. raciborskii was found in Gazan Dam Lake water with two morphotypes (coiled and straight). The appearance and cell density of this species was significantly positively related to high temperature and high ammonium concentrations, and negatively with nitrate and phosphate concentrations in the lake. Intracellular concentrations of CYN (4–173 μg L^?1) were associated with C. raciborskii rather than other cyanobacteria with a maximal value obtained in June 2011, coinciding with the highest bloom of this species (19?×?10⁷ trichome L^?1). CYN cell quotas (0.6–14.6 pg cell^?1) varied significantly along the study period and correlated with most environmental factors. The results of ELISA and liquid chromatography-mass spectrometry proved that the CYN production by strains of this species was isolated from this lake during the present study, with an amount reaching 568 μg g^?1. Extracellular CYN was also detected in cell-free lake water at concentrations 0.03–23.3 μg L^?1, exceeding the drinking water guideline value of 1 μg L^?1 during the Apr–Jul period. As this lake is an important source for drinking and irrigation waters, CYN monitoring should be included in the environmental and health risk assessment plans of these water bodies.     

Application of cold-induced aggregation microextraction as a fast,simple, and organic solvent-free method for the separation and preconcentration of Se(IV) in rice and various water samples

The developed method is based on cold-induced aggregation microextraction of Se(IV) using the 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid as an extractant followed by spectrophotometry determination. The extraction of Se(IV) was performed in the presence of dithizone as the complexing agent. In this method, a very small amount of 1-butyl-3-methylimidazolium hexafluorophosphate was added to the sample solution containing Se-dithizone complex. Then, the solution was kept in a thermostated bath at 50 °C for 4 min. Subsequently, the solution was cooled in an ice bath and a cloudy solution was formed. After centrifuging, the extractant phase was analyzed using a spectrophotometric detection method. Some important parameters that might affect the extraction efficiency were optimized (HCl, 0.6 mol L^?1; dithizone, 4.0?×?10^?6 mol L^?1; ionic liquid, 100 μL). Under the optimum conditions, good linear relationship, sensitivity, and reproducibility were obtained. The limit of detection (LOD) (3S_b/m) was 1.5 μg L^?1, and the relative standard deviation (RSD) was 1.2 % for 30 μg L^?1 of Se(IV). The linear range was obtained in the range of 5–60 μg L^?1. It was satisfactory to analyze rice and various water samples.     

Dissipation and residues of bispyribac-sodium in rice and environment

The dissipation and residues of bispyribac-sodium in rice cropping system were studied. Bispyribac-sodium residues were extracted by a simple analytical method based on QuEChERs and detected by LC-MS/MS. The limit of detection for bispyribac-sodium of this method was 0.375?×?10^?3 ng. The limit of quantification (LOQ) was 5.0 μg/kg for rice plant samples, 2.0 μg/kg for rice hull, 0.2 μg/kg for water, and 0.1 μg/kg for soil and husked rice samples. The average recoveries of bispyribac-sodium ranged from 74.7 to 108 %, with relative standard deviations less than 13 %. The half-lives of bispyribac-sodium in rice plant, water, and soil were in the range of 1.4–5.6 days. More than 90 % of bispyribac-sodium residue dissipated within 5 days. The final residues of bispyribac-sodium in rice were all below LOQ at harvest time.     

Assessment of physico-chemical qualities and heavy metal concentrations of Umgeni and Umdloti Rivers in Durban,South Africa

We assessed the effects of seasonal dynamics on the physico-chemical qualities and heavy metals concentrations of the Umgeni and Umdloti Rivers in Durban, South Africa. Water samples were taken from nine different sampling points and analysed for the following parameters; temperature, pH, turbidity, electrical conductivity (EC), biological oxygen demand (BOD₅), chemical oxygen demand (COD), phosphate (PO₄ ^2?), nitrate (NO₃ ^2?), ammonium (NH₄ ⁺), sulphate (SO₄ ^2?), lead (Pb²⁺), mercury (Hg²⁺), cadmium (Cd²⁺), aluminium (Al³⁺), and copper (Cu²⁺) using standard methods. The data showed variations it terms of the seasonal fluctuations and sampling regime as follows: temperature 12–26.5 °C; pH 5.96–8.45; turbidity 0.53–18.8 NTU; EC 15.8–5180 mS m^?1; BOD₅ 0.60–7.32 mg L^?1; COD 10.5–72.9 mg L^?1; PO₄ ^2??<?500–2,460 μg L^?1; NO₃ ^2? <0.05–4.21 mg L^?1; NH₄ ⁺?<?0.5–1.22 mg L^?1; SO₄ ^2? 3.90–2,762 mg L^?1; Pb²⁺ 0.023–0.135 mg L^?1; Hg²⁺ 0.0122–0.1231 mg L^?1 Cd²⁺ 0.068–0.416 mg L^?1; Al³⁺ 0.037–1.875 mg L^?1, and Cu²⁺0.006–0.144 mg L^?1. The concentrations of most of the investigated parameters exceeded the recommended limit of the South African Guidelines and World Health Organization tolerance limits for freshwater quality. We conclude that these water bodies are potentially hazardous to public health and this highlights the need for implementation of improved management strategies of these river catchments for continued sustainability.     

Single drop microextraction and gas chromatography–mass spectrometry for the determination of diflufenican, mepanipyrim, fipronil, and pretilachlor in water samples

An analytical method for the determination of diflufenican, mepanipyrim, pretilachlor, and fipronil in water samples was developed using single drop microextraction in the direct immersion mode and gas chromatography–mass spectrometry. A factorial fractionated design of type 2^6–1 at two levels was performed, to study the influence of experimental variables such as ionic strength, pH, agitation speed, extraction time, drop volume, and sample volume. To establish the optimal conditions for the variables that were significant, a Doehlert design was performed. The optimum conditions of extraction were 1 μL of heptane immersed in 4.0 mL of sample with continuous agitation at 500 rpm for 30 min at room temperature. The developed method proved to have good linearity for the range studied. The detection limits were 0.07 μg L^?1 for diflufenican, 0.03 μg L^?1 for mepanipyrim, 0.08 μg L^?1 for pretilachlor, and 1.39 μg L^?1 for fipronil. The method was validated on river water samples, showing the absence of matrix effect and recoveries ranged from 90.1 to 107.8 %. The results show that the method developed is accurate, sensitive, rapid, simple, and low cost, so it is recommended for application in the analysis of these different classes of pesticides in water samples.     

Residual behavior of quizalofop ethyl on onion (Allium cepa L.)

Quizalofop ethyl, a phenoxy propionate herbicide, is used for postemergence control of annual and perennial grass weeds in broad-leaved crops in India. The experiments were designed to study the dissipation kinetics of quizalofop ethyl on onion for two seasons. A simple, rapid, and sensitive method for estimation of quizalofop ethyl residues in onion and soil was developed and validated. The recoveries of quizalofop ethyl residues from onion and soil at different spiking level range from 84.81 to 92.68 %. The limit of quantification of this method was found to be 0.01 μg g^?1. The risk assessment through consumption of the onion in comparison to its acceptable daily intake which is an important parameter for the safety of the consumer was also evaluated. Standardized methodology supported by recovery studies was adopted to estimate residues of quizalofop ethyl on onion and soil. The average initial deposits of quizalofop ethyl on onion were observed to be 0.25 and 0.33 mg kg^?1, following single application of the herbicide at 50 g active ingredient (a.i.) ha^?1 during 2009 and 2010, respectively. The half-life values (T _1/2) of quizalofop ethyl on onion crop were worked out to be 0.85 and 0.79 days, respectively, during 2009 and 2010. At harvest time, the residues of quizalofop ethyl on onion and soil were found to be below the determination limit of 0.01 mg kg^?1 following single application of the herbicide at 50 and 100 g a.i. ha^?1 for both the periods.     

UV/H2O2 oxidation of arsenic and terbuthylazine in drinking water

Arsenic is a widespread contaminant in the environment. The intake of water containing high concentrations of arsenic could have serious impact on human health, such as skin and lung cancer. In the European Union, thus, also in Italy, the arsenic limit in drinking water is 10 μg L^?1. Several water remediation treatment technologies are available for arsenic removal. For some processes, the removal efficiencies can be improved after an oxidation step. Most full-scale applications are based on conventional oxidation processes for chemical micropollutant removal. However, if water contains arsenic and refractory organic contaminants, the advanced oxidation processes could be considered. The aim of this work was to investigate the effectiveness of ultraviolet (UV) radiation alone and in combination with hydrogen peroxide for the oxidation of arsenic and terbuthylazine (TBA). The experimental tests were performed in groundwater at the laboratory scale (0.1 mg L^?1 As(III) and 10 μg L^?1 TBA). Hydrogen peroxide alone (15 mg L^?1) was ineffective on both arsenic and TBA oxidation; the 253.7-nm radiation alone did not oxidize arsenic(III), but photolyzed efficiently TBA (52 % removal yield at a UV dose of 1,200 mJ cm^?2). The UV/H₂O₂ advanced oxidation (UV dose 600–2,000 mJ cm^?2, 5–15 mg L^?1 H₂O₂) was the most effective process for the oxidation of both arsenic and TBA, with observed oxidation efficiencies of 85 and 94 %, respectively, with 5 mg L^?1 H₂O₂ and a UV dose of 2,000 mJ cm^?2.