Particulate matter levels in a South American megacity: the metropolitan area of Lima-Callao,Peru

The temporal and spatial trends in the variability of PM₁₀ and PM_2.5 from 2010 to 2015 in the metropolitan area of Lima-Callao, Peru, are studied and interpreted in this work. The mean annual concentrations of PM₁₀ and PM_2.5 have ranges (averages) of 133–45 μg m^?3 (84 μg m^?3) and 35–16 μg m^?3 (26 μg m^?3) for the monitoring sites under study. In general, the highest annual concentrations are observed in the eastern part of the city, which is a result of the pattern of persistent local winds entering from the coast in a south-southwest direction. Seasonal fluctuations in the particulate matter (PM) concentrations are observed; these can be explained by subsidence thermal inversion. There is also a daytime pattern that corresponds to the peak traffic of a total of 9 million trips a day. The PM_2.5 value is approximately 40% of the PM₁₀ value. This proportion can be explained by PM₁₀ re-suspension due to weather conditions. The long-term trends based on the Theil-Sen estimator reveal decreasing PM₁₀ concentrations on the order of ?4.3 and ?5.3% year^?1 at two stations. For the other stations, no significant trend is observed. The metropolitan area of Lima-Callao is ranked 12th and 16th in terms of PM₁₀ and PM_2.5, respectively, out of 39 megacities. The annual World Health Organization thresholds and national air quality standards are exceeded. A large fraction of the Lima population is exposed to PM concentrations that exceed protection thresholds. Hence, the development of pollution control and reduction measures is paramount.     

Spatial and seasonal distribution of 17 endocrine disruptor compounds in an urban estuary (Mondego River,Portugal): evaluation of the estrogenic load of the area

The Mondego River estuary demonstrates signs of pollution, but the levels of endocrine disrupting compounds (EDCs), such as the natural (17β-estradiol and estrone) and pharmaceutical (17α-ethynylestradiol) estrogens, xenoestrogenic industrial pollutants (4-octylphenol, 4-nonylphenol, and their mono- and diethoxylates and bisphenol A), phytoestrogens (formononetin, biochanin A, daidzein, and genistein), and sitosterol were either poorly or never measured in this area. Thus, to conclude about the influx of EDCs in this estuary, water samples were taken every 2 months, during 1 year (2010) in low tide, at eight sites distributed along the estuary. Water samples (1 L) were preconcentrated in the Oasis HLB cartridges and cleaned in silica cartridges before their analysis by GC-MS. In summer, potentially hazardous amounts of estrogens (≈26 ng L^?1), alkylphenols (≈11.5 μg L^?1), alkylphenolethoxylates (≈13 μg L^?1), and phytoestrogens (≈5.6 μg L^?1) were measured. These data suggest that changes in the hydrodynamics of the estuary coupled with the increase of water temperatures interfere with the amount of EDCs in the water. Complementary physicochemical parameters also point to high levels of anthropogenic pollution in this area. Globally, the estrogenic load, expressed in ethynylestradiol equivalents, attained 71.8 ng L^?1 demonstrating that, all together, the measured EDCs pose important health risks for both biota and humans.     

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.     

Profile of PAHs in the inhalable particulate fraction: source apportionment and associated health risks in a tropical megacity

The present study proposed to investigate the atmospheric distribution, sources, and inhalation health risks of polycyclic aromatic hydrocarbons (PAHs) in a tropical megacity (Delhi, India). To this end, 16 US EPA priority PAHs were measured in the inhalable fraction of atmospheric particles (PM₁₀; aerodynamic diameter, ≤10 μm) collected weekly at three residential areas in Delhi from December 2008 to November 2009. Mean annual 24 h PM₁₀ levels at the sites (166.5–192.3 μg m^?3) were eight to ten times the WHO limit. Weekday/weekend effects on PM₁₀ and associated PAHs were investigated. Σ₁₆PAH concentrations (sum of 16 PAHs analyzed; overall annual mean, 105.3 ng m^?3; overall range, 10.5–511.9 ng m^?3) observed were at least an order of magnitude greater than values reported from European and US cities. Spatial variations in PAHs were influenced by nearness to traffic and thermal power plants while seasonal variation trends showed highest concentrations in winter. Associations between Σ₁₆PAHs and various meteorological parameters were investigated. The overall PAH profile was dominated by combustion-derived large-ring species (85–87 %) that were essentially local in origin. Carcinogenic PAHs contributed 58–62 % to Σ₁₆PAH loads at the sites. Molecular diagnostic ratios were used for preliminary assessment of PAH sources. Principal component analysis coupled with multiple linear regression-identified vehicular emissions as the predominant source (62–83 %), followed by coal combustion (18–19 %), residential fuel use (19 %), and industrial emissions (16 %). Spatio-temporal variations and time-evolution of source contributions were studied. Inhalation cancer risk assessment showed that a maximum of 39,780 excess cancer cases might occur due to lifetime inhalation exposure to the analyzed PAH concentrations.     

Predicting Pesticide Volatility Through Coupled Above- and Belowground Multiphysics Modeling

Pesticides are applied to agricultural fields to control unwanted pests but can volatilize and be transported downwind by wind currents to create the potential for non-target organism exposure. Volatilization rates change through the growing season due to pesticide application timing, meteorological differences, and the differential flux rates from soil and vegetation matrices. Field studies quantifying pesticide volatility are expensive and cannot capture the semi-infinite parameter combinations of soil, crop, management, and meteorological conditions encountered under regional agronomic practices. A numerical approach was used to simulate pesticide dissipation above- and belowground to augment field and laboratory experimental observations. Above- and belowground physics are coupled into a single numerical tool using the COMSOL Multiphysics® software package with the current emphasis on pesticide volatility into air from soil and vegetation and resulting near field neighboring air concentrations. Comparison of simulation results against experimental observations for an insecticide (chlorpyrifos) applied to potato and alfalfa fields shows good agreement (R² 0.68–0.98). Chlorpyrifos volatility from plant surfaces drives the overall volatility within the first several days post application. The maximum volatility flux rate simulated and observed were 0.79 and 0.66 μg m^?2 s^?1 for the alfalfa trial and 2.72 and 2.17 μg m^?2 s^?1 for the potato field, respectively. This coupled multiphysics tool [computational fluid dynamics (CFD), mass transfer coefficients, and variably saturated flow in soil] can be used to estimate volatility flux rates of pesticides when little or no prior knowledge is available and for extrapolating field study observations to different and diverse scenarios.     

PAHs in PM2.5 in Zhengzhou: concentration,carcinogenic risk analysis,and source apportionment

Ambient air samples were collected at two different locations between 2011 and 2012 in Zhengzhou, China in order to assess the concentration level, health risks, as well as the sources of polycyclic aromatic hydrocarbons (PAHs) in particulate matter (PM_2.5). The mean annual levels of PM_2.5 observed at industry site and residential site were 172?±?121 and 160?±?72 μg m^?3, respectively, which were about five times the annual value of proposed PM_2.5 standard (35 μg m^?3) in China. The PM_2.5 in all daily samples (n?=?47) exceeds the proposed PM_2.5 standard in China (75 μg m^?3) at both industrial and residential sites. Seasonal variations of PM_2.5 showed a clear trend of winter?>?autumn?>?spring?>?summer at both sites. The total concentrations of 16 PM_2.5-associated PAHs ranged from 61?±?51 to 431?±?281 and 38?±?25 to 254?±?189 ng m^?3, with mean value of 176?±?233 and 111?±?146 ng m^?3 at industry and residential sites, respectively. The major species were fluoranthene, pyrene, chrysene, benzo[b]fluoranthene and benzo[k]fluoranthene, and the concentration levels of PAHs in PM_2.5 were higher in winter than those of other seasons at both sites. The annual mean values of toxicity equivalency concentrations of ∑₁₆PAHs in PM_2.5 were 22.8 and 13.5 ng m^?3 in industry and residential area, respectively. In this study, the risk level of adult citizens through inhalation exposure to PAHs was calculated. The average estimates of lifetime inhalation cancer risks were approximately 8.9?×?10^?7 and 6.3?×?10^?7 for industry and residential sites, respectively. The main sources of 16 PAHs from both diagnostic ratios and principle component analysis identified as vehicular emissions and coal combustion.     

Investigating toxic metal levels in popular edible fishes from the South Durban basin: implications for public health and food security

Contamination of the ocean by heavy metals may have ecosystem-wide implications because they are toxic even if present in trace levels, and the relative ease of their bioaccumulation by marine organisms may affect human health, primarily through consumption of contaminated fish. We evaluated metal concentrations in six different popular edible fish species and estimated the potential health risks from consumption of contaminated fish. There was no correlation between fish length and average metal accumulation although the fish species tended to accumulate significantly more Al and Zn (P?<?0.05) than any of the other metals. Significantly higher Mn concentrations were found in fish gills compared to other body parts in all fish species. Bronze seabream, Catface rockcod, and Slinger seabream had significantly higher mean Cr concentration in the liver than in either the tissues or gills. The highest concentration of Zn in fleshy tissue was in Horse mackerel (56.71 μg g^?1) followed by Bronze seabream (31.07 μg g^?1). Al levels ranged from 5.6 μg g^?1 in Atlantic mackerel to 35.04 μg g^?1 in Horse mackerel tissue while Cu and Cr concentrations were highest in the tissues of Horse mackerel (6.83 and 1.81 μg g^?1, respectively) followed by Santer seabream (3.15; 1.09 μg g^?1) and Bronze seabream (3.09; 1.30 μg g^?1), respectively. The highest tissue concentration of Mn was detected in Bronze seabream (8.23 μg g^?1) followed by Catface rockcod (6.05 μg g^?1) and Slinger seabream (5.21 μg g^?1) while Pb concentrations ranged from a high of 8.44 μg g^?1 in Horse mackerel to 1.09 μg g^?1 in Catface rockcod. However, the estimated potential health risks from fish consumption as determined by the target hazard quotient (THQ) and hazard index (HI) were significantly lower than 1, implying that metals were not present in sufficiently high quantities to be of any health and/or food and security concern in the studied fishes.     

Hazard assessment of metals in invasive fish species of the Yamuna River,India in relation to bioaccumulation factor and exposure concentration for human health implications

Monitoring of heavy metals was conducted in the Yamuna River considering bioaccumulation factor, exposure concentration, and human health implications which showed contamination levels of copper (Cu), lead (Pb), nickel (Ni), and chromium (Cr) and their dispersion patterns along the river. Largest concentration of Pb in river water was 392 μg L^?1; Cu was 392 μg L^?1 at the extreme downstream, Allahabad and Ni was 146 μg L^?1 at midstream, Agra. Largest concentration of Cu was 617 μg kg^?1, Ni 1,621 μg kg^?1 at midstream while Pb was 1,214 μg kg^?1 at Allahabad in surface sediment. The bioconcentration of Cu, Pb, Ni, and Cr was observed where the largest accumulation of Pb was 2.29 μg kg^?1 in Oreochromis niloticus and 1.55 μg kg^?1 in Cyprinus carpio invaded at Allahabad while largest concentration of Ni was 174 μg kg^?1 in O. niloticus and 124 μg kg^?1 in C. carpio in the midstream of the river. The calculated values of hazard index (HI) for Pb was found more than one which indicated human health concern. Carcinogenic risk value for Ni was again high i.e., 17.02?×?10^?4 which was larger than all other metals studied. The results of this study indicated bioconcentration in fish due to their exposures to heavy metals from different routes which had human health risk implications. Thus, regular environmental monitoring of heavy metal contamination in fish is advocated for assessing food safety since health risk may be associated with the consumption of fish contaminated through exposure to a degraded environment.     

Seasonal perspective of dietary arsenic consumption and urine arsenic in an endemic population

Exposure to arsenic in arsenic endemic areas is most remarkable environmental health challenges. Although effects of arsenic contamination are well established, reports are unavailable on probable seasonal variation due to changes of food habit depending on winter and summer seasons, especially for endemic regions of Nadia district, West Bengal. Complete 24-h diets, drinking–cooking water, first morning voided urine samples, and diet history were analyzed on 25 volunteers in arsenic endemic Chakdah block of Nadia district, once in summer followed by once in winter from the same participants. Results depicted no seasonal variation of body weight and body mass index. Arsenic concentration of source drinking and cooking water decreased (p?=?0.04) from 26 μg L^?1 in summer to 6 μg L^?1 in winter season. We recorded a seasonal decrease of water intake in male (3.8 and 2.5 L day ^?1) and female (2.6 and 1.2 L day^?1) participants from summer to winter. Arsenic intake through drinking water decreased (p?=?0.04) in winter (29 μg day^?1) than in summer (100 μg day^?1), and urinary arsenic concentration decreased (p?=?0.018) in winter (41 μg L^?1) than in summer (69 μg L^?1). Dietary arsenic intake remained unchanged (p?=?0.24) over the seasons. Hence, we can infer that human health risk assessment from arsenic needs an insight over temporal scale.     

Health risk assessment of mercury and arsenic associated with consumption of fish from the Persian Gulf

Concentrations of mercury and arsenic in fish from the Persian Gulf were determined by graphite furnace atomic absorption spectrometry. Concentrations of the metals in muscle samples were 0.049–0.402 μg g^?1 for mercury and 0.168–0.479 μg g^?1 for arsenic, with means of 0.133 and 0.312 μg g^?1, respectively. The maximum daily consumption rate (grams per day) and meal consumption limit (meals per month) was calculated to estimate health risks associated with fish consumption. According to the results, the maximum allowable consumption rate varies between 8–56 and 15–96 g/day base on mercury and arsenic content, respectively. The results of this study indicate that the concentration of mercury and arsenic is well below the maximum permissible levels for mercury (0.5 μg g^?1) and arsenic (6 μg g^?1) according to international standards.     

Mapping of fluoride endemic area and assessment of F−1 accumulation in soil and vegetation

The prevalence of fluorosis is mainly due to the consumption of more fluoride (F^?1) through drinking water, vegetables, and crops. The objective of the study was mapping of F^?1 endemic area of Newai Tehsil, Tonk district, Rajasthan, India. For the present study, water, soil (0–45 cm), and vegetation samples were collected from 17 villages. Fluoride concentration in water samples ranged from 0.3 to 9.8 mg/l. Out of 17 villages studied, the amounts of F^?1 content of eight villages were found to exceed the permissible limits. Labile F^?1 content and total F^?1 content in soil samples ranges 11.00–70.05 mg/l and 50.3–179.63 μg g^?1, respectively. F^?1 content in tree species was found in this order Azadirachta indica 47.32–55.76 μg g^?1 > Prosopis juliflora 40.16–49.63 μg g^?1 > Acacia tortilis 34.39–43.60 μg g^?1. While in case of leafy vegetables, F^?1 content order was Chenopodium album 54.23–98.42 μg g^?1 > Spinacea oleracea 30.41–64.09 μg g^?1 > Mentha arvensis 35.48–51.97 μg g^?1. The order of F^?1 content in crops was found as 41.04 μg g^?1 Pennisetum glaucum > 13.61 μg g^?1 Brassica juncea > 7.98 μg g^?1 Triticum sativum in Krishi Vigyan Kendra (KVK) farms. Among vegetation, the leafy vegetables have more F^?1 content. From the results, it is suggested that the people of KVK farms should avoid the use of highly F^?1 containing water for irrigation and drinking purpose. It has been recommended to the government authority to take serious steps to supply drinking water with low F^?1 concentration for the fluorosis affected villages. Further, grow more F^?1 hyperaccumulator plants in F^?1 endemic areas to lower the F^?1 content of the soils.     

Assessment of trace metals and porphyrins in excreta of Humboldt penguins (Spheniscus humboldti) in different locations of the northern coast of Chile

To add data on trace metal contamination of Humboldt penguins in the South Pacific, levels of trace metals (As, Hg, Pb, Cu, Zn, and Cd) and porphyrins (copro-, uro-, and proto-) in excreta of Humboldt penguins that inhabit some important nesting sites on the northern coast of Chile were determined. Fresh excreta were collected on Pan de Azúcar Island, Chañaral Island, and Cachagua Island, from December 2011 to January 2012. Concentration of metals was determined by flame atomic absorption spectrophotometry, whereas porphyrins levels were measured by fluorimetric analysis. Concentrations (dry weight) of Cu (199.67 μg g^?1), As (7.85 μg g^?1), and Pb (12.78 μg g^?1) were higher (p?≤?0.05) in Cachagua Island. Colonies from Pan de Azúcar Island showed the highest levels of Hg (0.76 μg g^?1), Cd (47.70 μg g^?1), and Zn (487.10 μg g^?1). Samples from Cachagua Island showed the highest (p?≤?0.05) levels of copro- (2.16 nmol g^?1), uro- (2.20 nmol g^?1), and protoporphyrins (2.23 nmol g^?1). There was a positive correlation between the metals As, Pb, and Cu with uro-, copro-, and protoporphyrins. The results indicated that penguin colonies from Cachagua Island are more exposed to metal contamination than penguin colonies from Pan de Azúcar and Chañaral Islands, thus being more likely to develop certain diseases caused by contamination with metals. Considering biomagnification, the metals detected in the excreta of Humboldt penguins can be a source of contamination from marine environments to terrestrial ecosystems, which could also affect other living organisms.     

Heavy metal in water and aquatic organisms from different intertidal ecosystems,Persian Gulf

Intertidal ecosystems are being damaged by anthropogenic activities, particularly in the developing countries. In this study, the load of heavy metals was determined in water, fish, shrimp, and crab collected from four intertidal ecosystems, including coral reef, rocky shore, mangrove forest, and muddy habitat along the Persian Gulf coasts. Generally, the sequence of metal accumulation in the water of coral reef and mangrove forest was Ni > Pb > V > Cd > As > Hg, whereas in muddy habitats and rocky shores, the sequence was Ni > Pb > V > Cd > Hg > As and Ni > V > Pb > As > Hg > Cd, respectively. Water of the coral reef had the highest level of Ni (97.44 μg l^?1), Pb (3.92 μg l^?1), V (10.42 μg l^?1), Cd (3.92 μg l^?1), As (1.87 μg l^?1), and Hg (0.74 μg l^?1). For the most part, the highest concentrations of the studied metals were found in the liver and the gills of Johnius belangerii and the hepatopancreas of Portunus pelagicus and Metapenaus affinis collected from the coral reef ecosystem.     

Coupling of solvent-based de-emulsification dispersive liquid–liquid microextraction with high performance liquid chromatography for simultaneous simple and rapid trace monitoring of 2,4-dichlorophenoxyacetic acid and 2-methyl-4-chlorophenoxyacetic acid

A simple, rapid, and efficient sample pretreatment technique, based on solvent-based de-emulsification dispersive liquid–liquid microextraction (SD-DLLME), followed by high performance liquid chromatography (HPLC) has been developed for simultaneous preconcentration and trace detection of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2-methyl-4-chlorophenoxyacetic acid (MCPA) in water and urine samples. Some parameters such as acidity of solution, the amount of salt, type, and volume of extraction solvents, type of disperser/de-emulsifier solvent, and its volume were investigated and optimized. Under optimum extraction conditions, the limits of detections (LODs) of this method for MCPA and 2,4-D were 0.2 and 0.6 μg L^?1 (based on 3S_b/m) in water and 0.4 and 1.6 μg L^?1 in urine, respectively. Furthermore, dynamic linear range of this method for MCPA and 2,4-D was 1–300 and 2–400 μg L^?1, repectively. Finally, the applicability of the proposed method was evaluated by extraction and determination of the herbicides in urine and different water samples.     

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.     

Removing arsenic from groundwater in Cambodia using high performance iron adsorbent

In Cambodia, groundwater has been contaminated with arsenic, and purification of the water is an urgent issue. From 2010 to 2012, an international collaborative project between Japan and Cambodia for developing arsenic-removing technology from well water was conducted and supported by the foundation of New Energy and Industrial Technology Development Organization, Japan. Quality of well water was surveyed in Kandal, Prey Veng, and Kampong Cham Provinces, and a monitoring trial of the arsenic removal equipment using our patented amorphous iron (hydr)oxide adsorbent was performed. Of the 37 wells surveyed, arsenic concentration of 24 exceeded the Cambodian guideline value (50 μg L^?1), and those of 27 exceeded the WHO guideline for drinking water (10 μg L^?1). Levels of arsenic were extremely high in some wells (>1,000–6,000 μg L^?1), suggesting that arsenic pollution of groundwater is serious in these areas. Based on the survey results, 16 arsenic removal equipments were installed in six schools, three temples, two health centers, four private houses, and one commune office. Over 10 months of monitoring, the average arsenic concentrations of the treated water were between 0 and 10 μg L^?1 at four locations, 10–50 μg L^?1 at eight locations, and >50 μg L^?1 at four locations. The arsenic removal rate ranged in 83.1–99.7 %, with an average of 93.8 %, indicating that the arsenic removal equipment greatly lower the risk of arsenic exposure to the residents. Results of the field trial showed that As concentration of the treated water could be reduced to <10 µg L^?1 by managing the As removal equipment properly, suggesting that the amorphous iron (hydr)oxide adsorbent has high adsorbing capacity for As not only in the laboratory environment but also in the field condition. This is one of the succeeding As removal techniques that could reduce As concentration of water below the WHO guideline value for As in situ.     

High-frequency nutrient monitoring to infer seasonal patterns in catchment source availability, mobilisation and delivery

To explore the value of high-frequency monitoring to characterise and explain riverine nutrient concentration dynamics, total phosphorus (TP), reactive phosphorus (RP), ammonium (NH₄-N) and nitrate (NO₃-N) concentrations were measured hourly over a 2-year period in the Duck River, in north-western Tasmania, Australia, draining a 369-km² mixed land use catchment area. River discharge was observed at the same location and frequency, spanning a wide range of hydrological conditions. Nutrient concentrations changed rapidly and were higher than previously observed. Maximum nutrient concentrations were 2,577 μg L^?1 TP, 1,572 μg L^?1 RP, 972 μg L^?1 NH₄-N and 1,983 μg L^?1 NO₃-N, respectively. Different nutrient response patterns were evident at seasonal, individual event and diurnal time scales—patterns that had gone largely undetected in previous less frequent water quality sampling. Interpretation of these patterns in terms of nutrient source availability, mobilisation and delivery to the stream allowed the development of a conceptual model of catchment nutrient dynamics. Functional stages of nutrient release were identified for the Duck River catchment and were supported by a cluster analysis which confirmed the similarities and differences in nutrient responses caused by the sequence of hydrologic events: (1) a build-up of nutrients during periods with low hydrologic activity, (2) flushing of readily available nutrient sources at the onset of the high flow period, followed by (3) a switch from transport to supply limitation, (4) the accessibility of new nutrient sources with increasing catchment wetness and hydrologic connectivity and (5) high nutrient spikes occurring when new sources become available that are easily mobilised with quickly re-established hydrologic connectivity. Diurnal variations that could be influenced by riverine processes and/or localised point sources were also identified as part of stage (1) and during late recession of some of the winter high flow events. Illustrated by examples from the Duck River study, we demonstrate that the use of high-frequency monitoring to identify and characterise functional stages of catchment nutrient release is a constructive approach for informing and supporting catchment management and future nutrient monitoring strategies.     

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.     

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.     

Stability of lysosomal membrane in Carcinus maenas acts as a biomarker of exposure to pharmaceuticals

The presence of pharmaceuticals in the environment is now a major concern given their potential adverse effects on organisms, particularly human beings. Because the feeding style and habitat of the crab Carcinus maenas make this species vulnerable to organic contaminants, it has been used previously in ecotoxicological studies. Lysosomal membrane stability (LMS) in crabs is a general indicator of cellular well-being and can be visualized by the neutral red retention (NRR) assay. LMS in crab hemolymph has been evaluated as a cellular biomarker of adverse effects produced by exposure to pharmaceutical compounds. Crabs were exposed in the laboratory to four different pharmaceuticals for 28 days in a semistatic 24-h renewal assay. Filtered seawater was spiked every 2 days with various concentrations (from 0.1 to 50 μg·L^?1) of caffeine, ibuprofen, carbamazepine, and novobiocin. Results showed that NRR time, measured at day 28, was significantly reduced (p?<?0.05) after exposure to environmental concentrations of each pharmaceutical (caffeine?=?15 μg·L^?1; carbamazepine?=?1 μg·L^?1; ibuprofen?=?5 μg·L^?1; and novobiocin?=?0.1 μg·L^?1) when compared with control organisms. The predicted “no environmental effect” concentration/measured environmental concentration results showed that the selected pharmaceuticals are toxic at environmental concentrations and need further assessment. LMS monitoring in crabs is a sensitive tool for evaluating exposure to concentrations of selected drugs under laboratory conditions and provides a robust tier 1 testing approach (screening biomarker) for rapid assessment of marine pollution and environmental impact assessments for analyzing pharmaceutical contamination in aquatic environments.