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.     

Hydrogeochemistry and water quality assessment of the Kor–Sivand Basin, Fars province, Iran

In order to assess the quality and suitability of waters in the Kor-Sivand river basin, 60 water samples from the Kor river and 90 water samples from wells in the basin were studied. Assessments were based on Piper's and Gibbs' diagrams for water quality, Food and Agricultural Organization's (FAO) guidelines, and US Salinity Laboratory diagram for water suitability. The results showed that the river water is of Ca-HCO(3) type, while well water is of Ca-Cl and Na-Cl type. Based on Gibbs' diagram, the source of soluble ions in the river water samples is the weathering of stones over which water flows, while evaporation was found to be the dominant process in the ion concentration of the well samples. According to the FAO Guidelines, the salinity of surface water for irrigation did not cause great restrictions; however, many of these waters could create potential permeability problems. In the groundwater samples, a high salt concentration is more important than the infiltration problem. Mg hazard values at some sites limit its use for agricultural purposes. One third of the river water samples and two thirds of well waters had more than 50% magnesium. Saturation indices showed that 94% of the analyzed water samples are supersaturated with calcite, aragonite, and dolomite. Based on the US Salinity Laboratory diagram, river water samples were classified as C(2)S(1) and C(3)S(1), while C(4)S(3), C(4)S(4), C(2)S(1), and C(3)S(1) were the most dominant classes in well samples. Some management practices necessary for sustainable development of water resources in the study area were discussed briefly, including appropriate selection of crops, adequate drainage, leaching, blending and cyclic use of saline water, proper irrigation method, and addition of soil amendment.     

Who plans for health improvement? SEA,HIA and the separation of spatial planning and health planning

This study examines whether there is active planning for health improvement in the English spatial planning system and how this varies across two regions using a combination of telephone surveys and focus group interviews in 2005 and 2010. The spatial planning profession was found to be ill-equipped to consider the health and well-being implications of its actions, whilst health professionals are rarely engaged and have limited understanding and aspirations when it comes to influencing spatial planning. Strategic Environmental Assessment was not considered to be successful in integrating health into spatial plans, given it was the responsibility of planners lacking the capacity to do so. For their part, health professionals have insufficient knowledge and understanding of planning and how to engage with it to be able to plan for health gains rather than simply respond to health impacts. HIA practice is patchy and generally undertaken by health professionals outside the statutory planning framework. Thus, whilst appropriate assessment tools exist, they currently lack a coherent context within which they can function effectively and the implementation of the Kiev protocol requiring the engagement of health professionals in SEA is not to likely improve the consideration of health in planning while there continues to be separation of functions between professions and lack of understanding of the other profession.     

Phosphate adsorption characteristics at the sediment–water interface and phosphorus fractions in Nansi Lake, China, and its main inflow rivers

Phosphorus fractions and phosphate adsorption characteristics of 16 sediments from a shallow freshwater lake (Nansi Lake, China) and its inflow estuaries were investigated. In the present study, the sediment phosphorus is fractionated into exchangeable P (exch-P), Al-P, Fe-P, Ca-P, organic P (OP), inorganic P (IP) and total P (TP). The results show that the total phosphorus (TP) content in the sediments ranges from 571.67 to 1,113.55 mg kg(-1), and calcium bound phosphorus (Ca-P) is the main fraction of IP. The biologically available phosphorus (BAP) ranges from 32.02 to 229.67 mg kg(-1) in the Nansi Lake sediments. Phosphate adsorption on the sediments mainly occurs within 10 h and is completed within 48 h. The content of native adsorbed phosphorus (omega(NAP)) varies greatly from 6.05 to 194.37 mg kg(-1), showing a significant correlation with the total maximal amount of phosphorus adsorbed (TQ(max)). Adsorption efficiency (m) ranges from 574.79 to 3,220.68 l kg(-1) and zero equilibrium phosphorus concentration (C(EPC)) ranges from 0.010 to 0.157 mg l(-1). After the South-to-North Water Diversion Project, the inherent phosphorus present in sediments will be a major threat to the diverted water quality and be a predominant factor determining the trophic status of the lake even if the external load is reduced.     

Consequences and Correctives Related to Lake Acidification, Liming and Mercury in Fish – A Case-Study for Lake Huljesjön, Sweden, Using the LakeWeb-model

This work exemplifies how a given lake (Lake Huljesjön, Sweden) would likely respond to changes in pH-values and to liming (a standard measure against anthropogenic acidification). The basic questions are: How would a liming influence pH? How long would the changes last? How would the changes influence the structure and function of lake ecosystems? The work uses a comprehensive lake ecosystem model, LakeWeb, which accounts for production, biomasses, predation, abiotic/biotic interactions of nine key functional groups of organisms, phytoplankton, bacterioplankton, two types of zooplankton (herbivorous and predatory), two types of fish (prey and predatory), zoobenthos, macrophytes and benthic algae. LakeWeb is a dynamic model and gives weekly variations. It has been critically tested using empirical data and regressions from many lakes. Those tests are not presented here but have shown that the model can capture typical functional and structural patterns in lakes very well. This gives credibility to the results presented in this work, which would be very costly to obtain in the traditional manner by extensive field studies in one or a few lakes. This work presents for the first time predictions at the ecosystem level of how functional groups of organisms (and not individual species) are likely to respond to acidification and liming. Two existing dynamic models, one for liming, the other for Hg-concentrations in fish, have been added to the LakeWeb-model. These two models have previously been tested and proven to yield good predictions. The results presented here indicate that there are several probable changes in the structure and function of the lake foodweb related to acidification and liming. The predicted changes in macrophyte cover will influence the predation pressure on fish, and thereby the fish biomass. Reductions in primary production at low pH-values will cause reductions in fish biomass. There are several interesting compensatory effects between factors that increase fish biomass and factors that tend to decrease the biomass. Such matters can be handled quantitatively by the LakeWeb-model.     

Environmental Contaminants in Blood, Hair, and Tissues of Ocelots from the Lower Rio Grande Valley, Texas, 1986–1997

The ocelot (Felis pardalis) isan endangered neotropical cat distributed within asmall range in the Lower Rio Grande Valley (LRGV), inTexas, U.S.A. Studies of the impacts of environmentalcontaminants in wild cats are few. Approximately onefourth of the estimated population (about 100) ofocelots in the LRGV was sampled to evaluate theimpacts of chlorinated pesticides, polychlorinatedbiphenyls, and trace elements on the population. Hairwas collected from 32 ocelots trapped between 1986–1992,and blood was collected from 20 ocelots trappedbetween 1993–1997. A few blood samples were obtainedfrom individuals recaptured two or three times. Tissue samples from 4 road-killed ocelots were alsoanalyzed. DDE, PCBs, and Hg were some of the mostcommon contaminants detected in hair and blood. MeanHg levels in hair ranged from 0.5 to 1.25 g g^-1 dw,Se from 1.5 to 3.48 g g^-1 dw, and Pb from 0.56 to26.8 g g^-1 dw. Mean DDE concentrations in plasma ranged from 0.005 g g^-1 ww to 0.153 g g^-1 ww, and PCBs ranged from 0.006 g g^-1 ww to 0.092 g g^-1 ww. Mean Hg levels in red blood cells rangedfrom 0.056 g g^-1 dw to 0.25 g g^-1 dw. Concentrations of DDE, PCBs, or Hg, did not increasesignificantly with age, although the highestconcentrations of DDE and Hg were found in olderanimals. Overall, concentrations of DDE, PCBs, and Hgwere low and at levels that currently do not pose anythreat to health or survival of the ocelot. This isfurther supported by good reproduction of the ocelotin the LRGV, where adult females averaged about 1.5kittens/litter. Thus, it seems that the current majorthreat to recovery of the ocelot in the LRGV may behabitat loss, although potential impacts of newgeneration pesticides, such as organophosphorus andcarbamate insecticides need further study.     

Erosivity, surface runoff, and soil erosion estimation using GIS-coupled runoff–erosion model in the Mamuaba catchment, Brazil

This study evaluates erosivity, surface runoff generation, and soil erosion rates for Mamuaba catchment, sub-catchment of Gramame River basin (Brazil) by using the ArcView Soil and Water Assessment Tool (AvSWAT) model. Calibration and validation of the model was performed on monthly basis, and it could simulate surface runoff and soil erosion to a good level of accuracy. Daily rainfall data between 1969 and 1989 from six rain gauges were used, and the monthly rainfall erosivity of each station was computed for all the studied years. In order to evaluate the calibration and validation of the model, monthly runoff data between January 1978 and April 1982 from one runoff gauge were used as well. The estimated soil loss rates were also realistic when compared to what can be observed in the field and to results from previous studies around of catchment. The long-term average soil loss was estimated at 9.4 t ha^?1 year^?1; most of the area of the catchment (60 %) was predicted to suffer from a low- to moderate-erosion risk (<6 t ha^?1 year^?1) and, in 20 % of the catchment, the soil erosion was estimated to exceed >?12 t ha^?1 year^?1. Expectedly, estimated soil loss was significantly correlated with measured rainfall and simulated surface runoff. Based on the estimated soil loss rates, the catchment was divided into four priority categories (low, moderate, high and very high) for conservation intervention. The study demonstrates that the AvSWAT model provides a useful tool for soil erosion assessment from catchments and facilitates the planning for a sustainable land management in northeastern Brazil.     

Analysing urban expansion and land use suitability for the city of Kahramanmaraş, Turkey, and its surrounding region

This study aimed at quantifying changes in urban area of the city of Kahramanmara? (K.Mara?) between 1948 and 2006, and analysing suitability of existing land use (LU) to the land potential. Urban change information was derived from two black-white monoscopic aerial photographs, and IKONOS and the QuickBird images acquired in 1948, 1985, 2000 and 2006, respectively. QuickBird image and soil map with 1:25,000 scale were used to analyze suitability of the current LU pattern to the land potential. The findings showed that the urban area of K.Mara? has expanded approximately 13 times during the past six decades. According to current LU and the soil map, productive and moderately productive soils were largely (73.2%) allocated for agricultural activities, which means that there was a strong consistency between the agricultural LU type and the land capability. However, widespread agriculture on the non-productive soils, and urbanization on the fertile agricultural lands were assessed as unsuitable from sustainable LU viewpoint. Considering this phenomenon, it is possible to say that rapid urban expansion has a growing pressure on the fertile agricultural soils. Monitoring LU changes, particularly urbanization, and developing effective LU plans based on the land capability were determined as the most important approaches to encourage sustainable use of land.     

Monitoring The Turbidity and Surface Temperature Changes and Effects of the 17 August 1999 Earthquake in the İzmİt Gulf,Turkey by the Landsat TM/ETM Data

The temporal turbidity and surface temperature changes and effects of the 17 August 1999 earthquake in the İzmit Gulf, Turkey have been investigated using Landsat TM/ETM data. The gulf is in the Mediterranean–Black Sea transition climatic zone and is partially surrounded by green vegetation cover and degraded and densely urbanized-industrialized areas. Landsat TM/ETM data acquired in 1990–1999 confirms increase in turbidity. Turbidity is always low in the southern part and high in the northern part of the gulf, because the more urbanized and industrialized areas are located in the northern part. The Landsat-7 ETM data acquired in the same year (1999) shows seasonal changes in turbidity. Moreover, the two high turbidity and surface temperature anomalies, one of which is parallel to the 17 August 1999 earthquake surface rupture (east–west) and the other which is in the northwest–southeast direction were mapped from Landsat-5 TM data acquired the day (18.08.1999) following the earthquake in the east end of the gulf. On the basis of turbidity implying the sea bottom movement, it is possible to state that a second rupture in the northwest and southeast direction could have occurred at the sea bottom during the earthquake. The distribution of the seismicity centers and the orientation of the lineaments in the area support this finding.     

Distribution of heavy metals in the dissolved and suspended phase of the sea-surface microlayer, seawater column and in sediments of Singapore’s coastal environment

Concentrations of heavy metals were determined in the water column (including the sea-surface microlayer, subsurface, mid-depth and bottom water) and sediments from Singapore’s coastal environment. The concentration ranges for As, Cd, Cr, Cu, Ni, Pb and Zn in the seawater dissolved phase (DP) were 0.34–2.04, 0.013–0.109, 0.07–0.35, 0.23–1.16, 0.28–0.78, 0.009–0.062 and 0.97–3.66 μg L⁻¹ respectively. The ranges for Cd, Cr, Cu, Ni, Pb and Zn in the suspended particulate matter (SPM) were 0.16–0.73, 6.72–53.93, 12.87–118.29, 4.34–60.71, 1.10–6.08 and 43.09–370.49 μg g⁻¹, respectively. Heavy metal concentrations in sediments ranged between 0.054–0.217, 37.48–50.52, 6.30–21.01, 13.27–26.59, 24.14–37.28 and 48.20–62.36 μg g⁻¹ for Cd, Cr, Cu, Ni, Pb and Zn, respectively. The lowest concentrations of metals in the DP and SPM were most frequently found in the subsurface water while the highest concentrations were mostly observed in the SML and bottom water. Overall, heavy metals in both the dissolved and particulate fractions have depth profiles that show a decreasing trend of concentrations from the subsurface to the bottom water, indicating that the prevalence of metals is linked to the marine biological cycle. In comparison to data from Greece, Malaysia and USA, the levels of metals in the DP are considered to be low in Singapore. Higher concentrations of particulate metals were reported for the Northern Adriatic Sea and the Rhine/Meuse estuary in the Netherlands compared to values reported in this study. The marine sediments in Singapore are not heavily contaminated when compared to metal levels in marine sediments from other countries such as Thailand, Japan, Korea, Spain and China.     

Impact of mining and refining on the distribution and accumulation of nickel and other heavy metals in sediments of subarctic Lake Kuetsjärvi,Murmansk Region,Russia

Research on the influence of the activities of Pechenganickel Mining and Metallurgical Company on sediment heavy-metal geochemistry of the subarctic Lake Kuetsj?rvi (north-western Russia) are described. It is estimated that during 60 years of mining/refining activity, 310 t of Ni, 120 t of Cu, 14 t of Co, 19 t of Zn, 0.087 t of Cd, 0.78 t of Pb and 0.053 t of Hg have accumulated in the lake sediments. The latter can be a source of secondary pollution and represent a danger for the lake ecosystem. The sedimentation rate in the lake is estimated to be within the range of 1.5-3 mm year(-1). The average concentrations of Ni, Cu, Hg and Co in superficial sediments have increased 25, 14, 11 and 5 times, respectively in the last century.     

Exploring the multiplicity of soil–human interactions: organic carbon content,agro-forest landscapes and the Italian local communities

Environmental Monitoring and Assessment - Marine ecosystems provide many ecosystem goods and services. However, these ecosystems and the benefits they create for humans are subject to competing...     

The occurrence of glyphosate, atrazine, and other pesticides in vernal pools and adjacent streams in Washington, DC, Maryland, Iowa, and Wyoming, 2005–2006

Vernal pools are sensitive environments that provide critical habitat for many species, including amphibians. These small water bodies are not always protected by pesticide label requirements for no-spray buffer zones, and the occurrence of pesticides in them is poorly documented. In this study, we investigated the occurrence of glyphosate, its primary degradation product aminomethylphosphonic acid, and additional pesticides in vernal pools and adjacent flowing waters. Most sampling sites were chosen to be in areas where glyphosate was being used either in production agriculture or for nonindigenous plant control. The four site locations were in otherwise protected areas (e.g., in a National Park). When possible, water samples were collected both before and after glyphosate application in 2005 and 2006. Twenty-eight pesticides or pesticide degradation products were detected in the study, and as many as 11 were identified in individual samples. Atrazine was detected most frequently and concentrations exceeded the freshwater aquatic life standard of 1.8 micrograms per liter (microg/l) in samples from Rands Ditch and Browns Ditch in DeSoto National Wildlife Refuge. Glyphosate was measured at the highest concentration (328 microg/l) in a sample from Riley Spring Pond in Rock Creek National Park. This concentration exceeded the freshwater aquatic life standard for glyphosate of 65 microg/l. Aminomethylphosphonic acid, triclopyr, and nicosulfuron also were detected at concentrations greater than 3.0 microg/l.     

Trends of total cadmium, copper, and zinc in the zebra mussel (Dreissena polymorpha) along the upper reach of the St. Lawrence River: 1994—2005

This study examines spatial and temporal variability of bioaccumulation of cadmium, copper, and zinc in tissues of zebra mussels in the upper reach of the St. Lawrence River which originates at the outflow of Lake Ontario. It was hypothesized that concentrations of these metals in mussel tissues would decline over time and decrease with increasing distance from the outlet of Lake Ontario as a result of on-going efforts to reduce contaminant discharges into the lake. Size of mussels was also evaluated as a factor influencing bioaccumulation. Mussels were collected annually in October from six sites from 1994 to 2005, including one site near a local industry. Individuals were grouped into five or more size classes per site in each year. Soft tissues were analyzed for total cadmium, copper and zinc. Concentrations of cadmium and copper in tissues varied significantly both spatially and temporally. Cadmium concentrations were elevated at most sites; copper concentrations were moderately elevated compared with other studies in the Lake Ontario basin and St. Lawrence River. Zinc showed the most uniformity in mussels possibly due to internal regulation and to low levels of environmental exposure. Animal size correlated with copper concentrations of tissues in approximately 30% of samples but infrequently for cadmium and zinc. Cadmium and copper levels were found to decline downstream over time. Inter-annual variability of metal concentrations in mussel tissues suggests utilization in long-term monitoring programs to discern significant trends.     

Sediment Contamination, by Habitat, in the Tampa Bay Estuarine System (1993–1999): PAHs, Pesticides and PCBs

More than 760 Tampa Bay (Florida, U.S.A.) sediment samples have been analyzed for organic contaminants (PAHs, organochlorine pesticides, and PCBs) since 1993. Data were analyzed to assess status by habitat (defined by overlapping salinity zones and sediment type). The habitats most degraded by PAHs and pesticides were generally located in lower salinity, fine-grained sediment habitats, which are typically confined to the Hillsborough River. PCB contamination was more common in mesohaline waters of the Palm and Hillsborough rivers. Higher salinity portions of the bay, where medium to coarse sand-sized sediments predominate, showed little evidence of contamination by PAHs, PCBs and pesticides other than lindane.     

Comparative toxicity of nano-ZnO and bulk ZnO suspensions to zebrafish and the effects of sedimentation, ˙OH production and particle dissolution in distilled water

With the common application of nanoscale zinc oxide (nZnO) and significant potential for its release directly into aquatic environments, it is urgent to carry out research on ecotoxicological impact of nZnO. The characterization of nZnO, the amount of ˙OH in suspensions in the presence of light and the acute toxicity of nZnO and its bulk counterpart suspensions, as well as the acute toxicity of Zn(2+) solution to zebrafish (Danio rerio) at 96 h were studied. It was found that nZnO aggregated into irregular shapes in suspensions, and showed a relationship between its size distribution and concentration. In the presence of light, nZnO suspensions could generate ˙OH, the concentration of which increased with time. Although it was generally thought that ˙OH played a role in the biotoxicity to zebrafish, similar toxicity was observed for the nZnO and bulk ZnO suspensions (96 h LC(50) 3.969 mg L(-1), 2.525 mg L(-1), respectively). Furthermore, the sedimentation of nZnO and bulk ZnO in suspensions, and the accumulation of Zn in zebrafish were studied. The results showed that dissolved Zn(2+), from nZnO and bulk ZnO in suspensions, were toxic to zebrafish, while the aggregation and sedimentation of nZnO suspensions reduced the toxicity of nZnO. However, Zn(2+) may not be the main source of acute toxicity of nZnO and bulk ZnO to zebrafish. The experimental results highlight the importance of a systematic assessment of toxicity mechanisms of metal oxide nanoparticles (NPs) to determine definitively whether their toxicity is caused by nano-effects.     

Pool of mobile and immobile phosphorus in sediments of the large, shallow Lake Peipsi over the last 100?years

Temporal variations in sediment phosphorus (P) composition and mobility were estimated in surface sediments of accumulation (core PS509 44?cm) and erosion (core PS2009 30?cm) areas of the shallow, large Lake Peipsi sensu stricto (s.s.; 2611?km(2), unregulated water level). The P pool in sediments including buried and mobile P is evaluated for the first time, which will provide baseline data for the future modelling of internal loading in L. Peipsi. Five sedimentary P fractions (including inorganic and nonreactive P) were separately quantified: loosely adsorbed and pore-water P (NaCl-P); redox-sensitive fraction P (NaBD-P); P bound to oxides of non-reducible Fe and Al (NaOH-P); calcium-bound P, mainly from apatite minerals (HCl-P) and refractory, mainly organic P (Res-P). Concentrations of P fractions varied during the 100?years with the highest values around 2007-2008 and 1923-1935. The P in "active" layers that are available for bacteria and algae or those undergoing changes and diagenetic transformations in the sediment could follow sediments with the water content of ～88%. Potentially mobile P is not decreased in the sediments deposited 50-100?years ago and makes up ca 63?mg?m(-2)?y(-1) (with range 8.3-23.7% of the total P (TP)) in the accumulation area, and ca 0.047?mg?cm(-3) (with range 1.3-22.4% of TP) in the erosion area. The result shows that 13-60% of TP contained in the surface sediment (from 34 to 398?mg P m(-2) y(-1)) has been remobilised during accumulation and could be exported to the overlying water.