Simultaneous analysis of endosulfan, chlorpyrifos, and their metabolites in natural soil and water samples using gas chromatography-tandem mass spectrometry

Analysis of endosulfan, chlorpyrifos, and their nonpolar metabolites in extracts from environmental aqueous and soil samples was performed using a gas chromatography-tandem mass spectrometry (GC–MS/MS) technique. Full-scan GC–MS analysis showed poor sensitivity for some of the metabolites (endodiol and endosulfan ether). A multisegment MS/MS method was developed and MS/MS parameter isolation time, excitation time, excitation voltage, and maximum excitation energy were optimized for chosen precursor ions to enhance selectivity and sensitivity of the analysis. The use of MS/MS with optimized parameters quantified analytes with significantly higher accuracy, and detection limits were lowered to ~1/6th compared with the full-scan method. Co-eluting compounds, chlorpyrifos and chlorpyrifos oxon, were also analyzed successfully in the MS/MS mode by choosing exclusive precursor ions. Analysis of soil and water phase samples from contaminated soil slurry bioreactors showed that the MS/MS method could provide more reliable estimates of these pesticide and metabolites (especially those present in low concentrations) by annulling interferences from soil organic matter.     

Suspended particulate matter estimates using optical and acoustic sensors: application in Nestos River plume (Thracian Sea,North Aegean Sea)

The present study investigates the use of combined methods of optical and acoustic sensors, in collaboration with direct in situ measurements, for the calibration and validation of a model transforming acoustic backscatter intensity series into suspended particulate matter (SPM) concentration datasets. The model follows previously elaborated techniques, placing particular attention to the parameterization of the acoustic absorption index as a function of water physical properties. Results were obtained from the annual deployment (during 2007–2008) of an upward-facing acoustic Doppler current profiler (ADCP) (307 kHz), equipped with a Wave Array, and an optical backscatter sensor (OBS), at the bottom of Thassos Passage near Nestos River plume (Thracian Sea, Northern Greece). The OBS was calibrated through linear regression, using 2007 and 2012 field sampling data, exhibiting an error of 13–14 % due to chlorophyll presence. The ADCP signal was calibrated through simultaneous measurements of backscatter intensity and turbidity profiles. Harmonic analysis on the model-produced SPM concentrations explained the tidal influence on their variability, especially during the summer. Empirical orthogonal functions analysis revealed the impact of waves and wave-induced currents on SPM variability. Finally, Nestos River sediment load was found uncorrelated to the SPM change in Thassos Passage, due to the dispersal and sediment deposition near the river mouth.     

Feasibility study of rainwater harvesting system in Sylhet City

In rural areas in Bangladesh, groundwater is the principal source of water supply. This underground water is available in considerable amount in shallow aquifers. It is free from pathogenic microorganisms and hence water-borne diseases. In plain lands, other than hilly areas, water supply to 97% rural population comes from tube-wells, which is regarded to be a phenomenal achievement in preserving public health. Besides, a dependable water supply system all throughout the country is offset by two factors: (a) high salinity in surface plus groundwater in coastal areas; (b) want of suitable groundwater aquifers in hilly areas and the high cost of setting up tube-wells due to deep underground water table and stony layers. However, presence of arsenic in underground water now poses a serious threat to the success once made in water supply by setting up of manually operated tube-wells in the village areas—the achievement is now on the brink of total collapse. In about 61 districts out of 64, presence of arsenic exceeds a quantity of 0.05 mg/1, a permissible limit as per Bangladeshi water quality standard. Harvesting rainwater can be a pragmatic solution to this problem, which is common in many places in Sylhet especially in the hilly areas on the north eastern part of the city. This can be an alternative source of drinking water because of availability of rainwater from March to October. Heavy rain occurs from end of May till mid September, which is commonly known as the rainy season. This paper focuses on the possibility of harvesting rainwater in rural communities and thickly populated urban areas of Sylhet. It also demonstrates the scopes of harvesting rainwater using simple and low-cost technology. With setting up of a carefully planned rainwater storage tank, a family can have all of its drinking water from rain. Planned use of rainwater through rainwater harvesting in the roof catchments may fulfill the entire annual domestic water demand of a family in the rural areas of Bangladesh.     

Numerical Modeling of a Potential Geological CO 2 Sequestration Site at Minden (Germany)

We study opportunities for CO₂ sequestration in geological formations of the state North Rhine Westphalia in Germany. Simulations are performed for evaluating a potential site within the Bunter sandstone formation near the town of Minden in a depth?of around 3,000 m using the numerical simulator TOUGHREACT. Our focus is on three CO₂ storage mechanisms: (1) hydrodynamic trapping, (2) dissolution trapping, and (3) mineral trapping. The results show that due to buoyancy the injected CO₂ phase initially migrates towards the top of the reservoir and is hydrodynamically trapped beneath the confining layer of the cap rock. Then, the CO₂ spreads laterally and dissolves partially in the formation water. The dissolution of CO₂ results in an increase of the density of the brine causing a downward migration until it settles after 10,000 years at the bottom of the reservoir. The simulations indicate that after 10,000 years, 15% (17 Mt) from a total of 114 Mt injected CO₂ are trapped hydrodynamically, 20% (23 Mt) are trapped by dissolution, and 65% (74 Mt) are fixed in newly formed carbonates such as dawsonite, ankerite, and siderite. Within our study pressure increases near the injection well by a factor of 1.1 which is lower than the upper limit usually accepted in gas storage operations. The mineral reactions cause a net decrease of porosity and in turn a decrease of permeability down to 9% of the initial value in parts of the reservoir.     

Vegetation NDVI Linked to Temperature and Precipitation in the Upper Catchments of Yellow River

Vegetation in the upper catchment of Yellow River is critical for the ecological stability of the whole watershed. The dominant vegetation cover types in this region are grassland and forest, which can strongly influence the eco-environmental status of the whole watershed. The normalized difference vegetation index (NDVI) for grassland and forest has been calculated and its daily correlation models were deduced by Moderate Resolution Imaging Spectroradiometer products on 12 dates in 2000, 2003, and 2006. The responses of the NDVI values with the inter-annual grassland and forest to three climatic indices (i.e., yearly precipitation and highest and lowest temperature) were analyzed showing that, except for the lowest temperature, the yearly precipitation and highest temperature had close correlations with the NDVI values of the two vegetation communities. The value of correlation coefficients ranged from 0.815 to 0.951 (p?<?0.01). Furthermore, the interactions of NDVI values of vegetation with the climatic indicators at monthly interval were analyzed. The NDVI of vegetation and three climatic indices had strong positive correlations (larger than 0.733, p?<?0.01). The monthly correlations also provided the threshold values for the three climatic indictors, to be used for simulating vegetation growth grassland under different climate features, which is essential for the assessment of the vegetation growth and for regional environmental management.     

Interlaboratory evaluation of trace element determination in workplace air filter samples by inductively coupled plasma mass spectrometry

Inductively coupled plasma mass spectrometry (ICP-MS) is becoming more widely used for trace elemental analysis in the occupational hygiene field, and consequently new ICP-MS international standard procedures have been promulgated by ASTM International and ISO. However, there is a dearth of interlaboratory performance data for this analytical methodology. In an effort to fill this data void, an interlaboratory evaluation of ICP-MS for determining trace elements in workplace air samples was conducted, towards fulfillment of method validation requirements for international voluntary consensus standard test methods. The study was performed in accordance with applicable statistical procedures for investigating interlaboratory precision. The evaluation was carried out using certified 37-mm diameter mixed-cellulose ester (MCE) filters that were fortified with 21 elements of concern in occupational hygiene. Elements were spiked at levels ranging from 0.025 to 10 μg filter(-1), with three different filter loadings denoted "Low", "Medium" and "High". Participating laboratories were recruited from a pool of over fifty invitees; ultimately twenty laboratories from Europe, North America and Asia submitted results. Triplicates of each certified filter with elemental contents at three different levels, plus media blanks spiked with reagent, were conveyed to each volunteer laboratory. Each participant was also provided a copy of the test method which each participant was asked to follow; spiking levels were unknown to the participants. The laboratories were requested to prepare the filters by one of three sample preparation procedures, i.e., hotplate digestion, microwave digestion or hot block extraction, which were described in the test method. Participants were then asked to analyze aliquots of the prepared samples by ICP-MS, and to report their data in units of μg filter(-1). Most interlaboratory precision estimates were acceptable for medium- and high-level spikes (RSD <25%), but generally yielded greater uncertainties than were anticipated at the outset of the study.     

Preparation, certification and interlaboratory analysis of workplace air filters spiked with high-fired beryllium oxide

Occupational sampling and analysis for multiple elements is generally approached using various approved methods from authoritative government sources such as the National Institute for Occupational Safety and Health (NIOSH), the Occupational Safety and Health Administration (OSHA) and the Environmental Protection Agency (EPA), as well as consensus standards bodies such as ASTM International. The constituents of a sample can exist as unidentified compounds requiring sample preparation to be chosen appropriately, as in the case of beryllium in the form of beryllium oxide (BeO). An interlaboratory study was performed to collect analytical data from volunteer laboratories to examine the effectiveness of methods currently in use for preparation and analysis of samples containing calcined BeO powder. NIST SRM(?) 1877 high-fired BeO powder (1100 to 1200 °C calcining temperature; count median primary particle diameter 0.12 μm) was used to spike air filter media as a representative form of beryllium particulate matter present in workplace sampling that is known to be resistant to dissolution. The BeO powder standard reference material was gravimetrically prepared in a suspension and deposited onto 37 mm mixed cellulose ester air filters at five different levels between 0.5 μg and 25 μg of Be (as BeO). Sample sets consisting of five BeO-spiked filters (in duplicate) and two blank filters, for a total of twelve unique air filter samples per set, were submitted as blind samples to each of 27 participating laboratories. Participants were instructed to follow their current process for sample preparation and utilize their normal analytical methods for processing samples containing substances of this nature. Laboratories using more than one sample preparation and analysis method were provided with more than one sample set. Results from 34 data sets ultimately received from the 27 volunteer laboratories were subjected to applicable statistical analyses. The observed performance data show that sample preparations using nitric acid alone, or combinations of nitric and hydrochloric acids, are not effective for complete extraction of Be from the SRM 1877 refractory BeO particulate matter spiked on air filters; but that effective recovery can be achieved by using sample preparation procedures utilizing either sulfuric or hydrofluoric acid, or by using methodologies involving ammonium bifluoride with heating. Laboratories responsible for quantitative determination of Be in workplace samples that may contain high-fired BeO should use quality assurance schemes that include BeO-spiked sampling media, rather than solely media spiked with soluble Be compounds, and should ensure that methods capable of quantitative digestion of Be from the actual material present are used.     

How Do River Nitrate Concentrations Respond to Changes in Land-use? A Modelling Case Study of Headwaters in the River Derwent Catchment,North Yorkshire,UK

A combined semi-distributed hydrological model (CASCADE/QUESTOR) is used to evaluate the steady-state that may be achieved after changes in land-use or management and to explore what additional factors need to be considered in representing catchment processes. Two rural headwater catchments of the River Derwent (North Yorkshire, UK) were studied where significant change in land-use occurred in the 1990s and the early 2000s. Much larger increases in mean nitrate concentration (55%) were observed in the catchment with significant groundwater influence (Pickering Beck) compared with the surface water-dominated catchment (13% increase). The increases in Pickering Beck were considerably greater than could be explained by the model in terms of land-use change. Consequently, the study serves to focus attention on the long-term increases in nitrate concentration reported in major UK aquifers and the ongoing and chronic impact this trend is likely to be having on surface water concentrations. For river environments, where groundwater is a source, such trends will mask the impact of measures proposed to reduce the risk of nitrate leaching from agricultural land. Model estimates of within-channel losses account for 15–40% of nitrate entering rivers.