Different hydrodynamic processes regulated on water quality (nutrients,dissolved oxygen,and phytoplankton biomass) in three contrasting waters of Hong Kong

The subtropical Hong Kong (HK) waters are located at the eastern side of the Pearl River Estuary. Monthly changes of water quality, including nutrients, dissolved oxygen (DO), and phytoplankton biomass (Chl-a) were routinely investigated in 2003 by the Hong Kong Environmental Protection Department in three contrasting waters of HK with different prevailing hydrodynamic processes. The western, eastern, and southern waters were mainly dominated by nutrient-replete Pearl River discharge, the nutrient-poor coastal/shelf oceanic waters, and mixtures of estuarine and coastal seawater and sewage effluent of Hong Kong, respectively. Acting in response, the water quality in these three contrasting areas showed apparently spatial–temporal variation pattern. Nutrients usually decreased along western waters to eastern waters. In the dry season, the water column was strongly mixed by monsoon winds and tidal currents, which resulted in relatively low Chl-a (<5 μg l^?1) and high bottom DO (>4 mg l^?1), suggesting that mixing enhanced the buffering capacity of eutrophication in HK waters. However, in the wet season, surface Chl-a was generally >10 μg l^?1 in southern waters in summer due to halocline and thermohaline stratification, adequate nutrients, and light availability. Although summer hypoxia (DO <2 mg l^?1) was episodically observed near sewage effluent site and in southern waters induced by vertical stratification, the eutrophication impacts in HK waters were not as severe as expected owing to P limitation and short water residence time in the wet season.     

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.     

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.     

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.     

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.     

Sediments as a potential tool for assessment of sewage pollution in Barigüi River, Brazil

Sediments constitute a pollutant trap and have proven to be an efficient tool to identify environmental impacts. Sediments are considered a very important means to assess the level of contamination of water bodies because of their ability to accumulate metals and organic. The anthropogenic inputs of sewage, with or without prior treatment, in aquatic environments, affect the geochemical composition of sediment. In addition, the sediment adsorbs hydrophobic compounds found in feces, such as the fecal sterols. The granulometric and geochemical composition of the sediment of Barigüi River-Brazil was investigated. The results show that silt and clay dominate the granulometric composition of the sediments. The geochemical composition of sediments showed high concentrations of phosphorus and nitrogen. The Redfield ratios confirm the inputs of phosphorus and nitrogen. The TOC/N ratio was used to identify the source of pollution. N/TP ratios were found between 1.0 and 3.5. Clearly, an input of phosphorus, sewage is the most acceptable source, following the historic profile of the Barigüi River. High concentration of nitrogen phosphorus labels the area to be polluted by sewage. To confirm the sewage pollution, adsorbed fecal sterols in sediments were investigated. The concentration of total sterols was found between 0.86 and 304.58 μg g^???1. Two distinguished scenario was found, one severely polluted and another slightly polluted. The highest concentrations of total fecal sterols were associated with sediment whose geochemical composition showed higher levels of TOC, as well as higher proportions of silt and clay. Also, epicoprostanol, a coprostanol isomer, was used as an indicator of the level of treatment or age of the fecal matter because it is formed during the treatment of wastewater and sludge digestion. If the treatment of sludge takes a long time, epicoprostanol can form from cholesterol, and relative proportions of those compounds may be used as an indicator of the presence of untreated sewage in the sediments. The epicoprostanol was found in the range between 0.02 and 9.71 μg g^???1; concentration of up to 0.015 μg g^???1 represents situations where there is strong contamination by sewage. All sites investigated showed a concentration of epicoprostanol higher than the value adopted as threshold. The lower concentration of epicoprostanol found for all sites is consistent with the high concentration found for coprostanol, and this is typical for untreated sewage.     

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.     

A preliminary study on the occurrence and behavior of carbamazepine (CBZ) in aquatic environment of Yangtze River Delta, China

The occurrence and behavior of carbamazepine (CBZ) was investigated in aquatic environment of Yangtze River Delta, East China. The water samples were enriched by solid-phase extraction and analyzed by high-performance liquid chromatography with diode array detector. The validation of the analytical method included linearity (0.1?C1 mg/L), recovery studies, and determination of limits of quantification. Limits of quantification of CBZ in various aquatic samples were in the range of 0.1?C0.2 ??g/L. CBZ was detected in the Tongji University Intramural River, the Huangpu River, and the Suzhou River with the highest concentration of 1,090 ng/L, but not detected in the Nanhengyin River and the Caojia River. In sewage water samples, CBZ was not detected in one of the sewage treatment plants (STPs) but was detected in the raw influents and effluents at the other three selected STPs in Shanghai, with the concentrations ranging from 230 to 1,110 ng/L. CBZ was not completely eliminated after secondary treatment (with the active sludge process).     

Assessment of bioavailable fraction of POPS in surface water bodies in Johannesburg City,South Africa,using passive samplers: an initial assessment

In this study, the semipermeable membrane device (SPMD) passive samplers were used to determine freely dissolved concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in selected water bodies situated in and around Johannesburg City, South Africa. The devices were deployed for 14 days at each sampling site in spring and summer of 2011. Time weighted average (TWA) concentrations of the water-borne contaminants were calculated from the amounts of analytes accumulated in the passive samplers. In the area of interest, concentrations of analytes in water ranged from 33.5 to 126.8 ng l^?1 for PAHs, from 20.9 to 120.9 pg l^?1 for PCBs and from 0.2 to 36.9 ng l^?1 for OCPs. Chlorinated pesticides were mainly composed of hexachlorocyclohexanes (HCHs) (0.15–36.9 ng l^?1) and dichlorodiphenyltrichloromethane (DDT) with its metabolites (0.03–0.55 ng l^?1). By applying diagnostic ratios of certain PAHs, identification of possible sources of the contaminants in the various sampling sites was performed. These ratios were generally inclined towards pyrogenic sources of pollution by PAHs in all study sites except in the Centurion River (CR), Centurion Lake (CL) and Airport River (AUP) that indicated petrogenic origins. This study highlights further need to map up the temporal and spatial variations of these POPs using passive samplers.     

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.     

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.     

Distribution of phthalate esters in topsoil: a case study in the Yellow River Delta, China

The Yellow River Delta (YRD) is a typical agricultural and petrochemical industrial area of China. To assess the current status of phthalate esters (PAEs) of soil residues, soil samples (0～20 cm) (n?=?82) were collected in Bincheng District, at the geographic center of the YRD. PAEs were detected in all topsoil samples analyzed, which indicated that PAEs are ubiquitous environmental contaminants. Concentrations of 11 PAEs are in the range of 0.794～19.504 μg g^?1, with an average value of 2.975 μg g^?1. It was presented that PAEs pollution in this area was weak and monotonously increasing along the rural–urban gradient. Higher concentrations were observed from roadsides (and/or gutters), densely anthropogenic activities areas (such as the urbanization and industrialization), and agriculture influence district, which mainly originated from construction waste, municipal sewage, agricultural waste and pesticide, discarded plastic effusion and atmospheric depositions. Concentrations of PAEs were weakly positivity correlated with soil organic carbon content and pH, which suggested both of them can affect the distribution of PAEs. The concentration of di (2-ethylhexyl) phthalate and di-n-butyl phthalate dominated in the 11 PAEs, with the average values of 0.735 and 1.915 μg g^?1, respectively, and accounted for 92.1 % of the whole PAEs’ concentrations. No significant differences of PAE congeneric profiles were observed between our work and others previously reported, which is consistent with the use of similar commercial PAEs around the world.     

Dissolved inorganic nutrients and chlorophyll a in an estuary receiving sewage treatment plant effluents: Cachoeira River estuary (NE Brazil)

Sampling was conducted monthly during a transition period between the dry and rainy seasons in order to evaluate the effectiveness of a municipal sewage treatment plant (STP) in eutrophication control. STP effluent and fluvial input data were also estimated. In the dry period, high concentrations of nutrients, chlorophyll a (up to 360 μg?L^?1), and anoxia in bottom waters were observed in the upper portion of the estuary. Nitrate was scarce during the dry months, although high concentrations were observed at the river sources and the upper estuary. The N:P and Si:P molar ratios were usually below 16:1, and the Si:N ratio was higher than 1:1. The fluvial inputs were a greater source of nutrients to the estuary than the STP, but nutrient loading by these effluents were also important in contributing to the eutrophication of the upper estuarine zone, especially in the dry season when symptoms were more intense.     

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.     

Insecticide residues in soil and water in coastal areas of vegetable production in Togo

Some common organochlorine, organophosphorus and pyrethroid insecticides were analysed in agricultural soil samples (n?=?35) and surface water and groundwater samples (n?=?25) collected from coastal areas of vegetable production in Togo. Analytical methods included solvent extraction of the insecticide residues and their subsequent quantification using GC-ECD. δ-HCH, heptachlor epoxide, 4,4-DDE, endosulphan (α, β and sulphate), lambda-cyalothrin and chlorpyrifos were found in the soil samples with concentrations that varied from non-detectable (ND) to 26.93 μg kg^?1 dry weight. For water samples, heptachlor epoxide, 2,4-DDD, 4,4-DDD, 4,4-DDE and endosulphan (α, β, and sulphate) were found at contamination levels that varied from ND to 0.116 μg L^?1. The concentration of insecticide residues detected in the water samples was below the limits set by the World Health Organization (WHO) and also by the European Union (EU), with the exception of the concentration of endosulphan sulphate at the Aného site, which was 0.116 μg L^?1.     

Examining spatial patterns in polycyclic aromatic compounds measured in stream macroinvertebrates near a small subarctic oil and gas operation

The Cameron River runs through a small, remote petrochemical development in the Cameron Hills (Northwest Territories, Canada). In order to evaluate the exposure of aquatic biota to contaminants from oil and gas activities, we measured polycyclic aromatic compounds (PACs) in macroinvertebrates collected from sites and tributaries along the Cameron River, including upstream and downstream of the development, and sites located near drilled wells (developed). Macroinvertebrate tissue PAC burdens ranged from 0.2–2.8 μg g^?1 lipid for unsubstituted compounds, and from 4.2–63.2 μg g^?1 lipid for alkylated compounds, relatively low compared to similar studies from more industrialized regions in North America. There was no significant difference in tissue PAC burdens between upstream, downstream, or developed sites (p?=?0.12), although alkyl PACs in five out of seven developed sites were higher than the regional average. Petrogenic PACs were dominant in most samples, including alkyl fluorines, alkyl phenanthrene/anthracenes, and alkyl dibenzothiophenes. Minimal changes in PAC composition in macroinvertebrate tissues were detected along the Cameron River, with the exception of the two sites furthest downstream that had high concentrations of C3-C4 naphthalene. Overall, our results suggest that oil and gas development in the Cameron Hills has not resulted in substantial increases in PAC bioaccumulation in stream macroinvertebrates, although the potential that alkyl naphthalenes are being transported downstream from the development warrants further attention.     

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.     

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.     

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.     

Extraction of ultra traces of polychlorinated biphenyls in aqueous samples using suspended liquid-phase microextraction and gas chromatography-electron capture detection

This study reports the feasibility of applying directly suspended liquid-phase microextraction (DSLPME)-gas chromatography detection for the pre-concentration and determination of low levels of eight polychlorinated biphenyls (PCBs) in aqueous samples. The technique requires minimal sample preparation, analysis time and solvent consumption and represents significant advantages over conventional analytical methods. The experimental parameters such as salt content, sample temperature, stirring rate, extraction time, micro-drop volume and breakthrough volume were investigated and found to have significant influences on DSLPME. Under the optimal experimental conditions, the enrichment factor ranged from 578 to 729, and the recovery was above 93 %. Calibration curves possessed good linearity (R ²?>?0.99) over a wide concentration range of 0.1–10.0 μg L^?1 with limits of detection ranging from 0.01 to 0.07 μg L^?1. The relative standard deviations for 1.0 μg L^?1 of PCBs in water by using internal standard were in the range 2–14 % (n?=?3). The proposed simple, accurate and sensitive analytical method was applied successfully to the determination of trace amounts of PCBs in water samples.