Analysing the sensitivity behaviour of two hydrology models

Recently, the New Morris Method has been presented as an effective sensitivity analysis tool for mathematical models. The New Morris Method estimates the sensitivity of an output parameter to a given set of input parameters (first-order effects) and the extent these parameters interact with each other (second-order effects). This method requires the specification of two parameters (runs and resolution) that control the sampling of the output parameter to determine its sensitivity to various inputs. The criteria for these parameters have been set on the analysis of a well-behaved analytical function (see Cropp and Braddock, Reliab. Eng. Syst. Saf. 78:77–83, 2002), which may not be applicable to other physical models that describe complex processes. This paper will investigate the appropriateness of the criteria from (Cropp and Braddock, 2002) and hence the effectiveness of the New Morris Method to determine the sensitivity behaviour of two hydrologic models: the Soil Erosion and Deposition System and Griffith University Representation of Urban Hydrology. In the first case, this paper will separately analyse the sensitivity of an output parameter on a set of input parameters (first- and second-order effects) for each model and discuss the physical meaning of these sensitivities. This will be followed by an investigation into the sampling criteria by exploring the convergence of the sensitivity behaviour for each model as the sampling of the parameter space is increased. By comparing these trends to the convergence behaviour from Cropp and Braddock (2002), we will determine how well the New Morris Method estimates the sensitivity for each model and whether the sampling criteria are appropriate for these models. It will be shown that the New Morris Method can provide additional insight into the functioning of these models, and that, under a different metric, the sensitivity behaviour of these models does converge confirming the sampling criteria set by Cropp and Braddock.     

Arsenic speciation in human hair: a new perspective for epidemiological assessment in chronic arsenicism

The analysis for arsenic in hair is commonly used in epidemiological studies to assess exposure to this toxic element. However, poor correlation between total arsenic concentration in hair and water sources have been found in previous studies. Exclusive determination of endogenous arsenic in the hair, excluding external contamination has become an analytical challenge. Arsenic speciation in hair appears as a new possibility for analytical assessing in As-exposure studies. This study applied a relative simple method for arsenic speciation in human hair based on water extraction and HPLC-HG-ICP-MS. The concentration of arsenic species in human hair was assessed in chronically As(V)-exposed populations from two villages (Esqui?a and Illapata) of the Atacama Desert, Chile. The arsenic concentrations in drinking water are 0.075 and 1.25 mg L(-1), respectively, where As(V) represented between 92 and 99.5% of the total arsenic of the consumed waters. On average, the total arsenic concentrations in hair from individuals of Esqui?a and Illapata were 0.7 and 6.1 microg g(-1), respectively. Four arsenic species, As(III), DMA(V), MMA(V) and As(V), were detected and quantified in the hair extracts. Assuming the found species in extracts represent the species in hair, more than 98% of the total arsenic in hair corresponded to inorganic As. On average, As(III) concentrations in hair were 0.25 and 3.75 microg g(-1) in Esqui?a and Illapata, respectively; while, the As(V) average concentrations were 0.15 and 0.45 microg g(-1) in Esqui?a and Illapata, respectively. Methylated species represent less than 2% of the extracted As (DMA(V)+ MMA(V)) in both populations. As(III) in hair shows the best correlation with chronic exposure to As(V) in comparison to other species and total arsenic. In fact, concentrations of As(total), As(III) and As(V) in hair samples are correlated with the age of the exposed individuals from Illapata (R= 0.65, 0.69, 0.57, respectively) and with the time of residence in this village (R= 0.54, 0.71 and 0.58, respectively).     

High frequency monitoring of the coastal marine environment using the MAREL buoy

The MAREL Iroise data buoy provides physico-chemical measurements acquired in surface marine water in continuous and autonomous mode. The water is pumped 1.5 m from below the surface through a sampling pipe and flows through the measuring cell located in the floating structure. Technological innovations implemented inside the measuring cell atop the buoy allow a continuous cleaning of the sensor, while injection of chloride ions into the circuit prevents biological fouling. Specific sensors for temperature, salinity, oxygen and fluorescence investigated in this paper have been evaluated to guarantee measurement precision over a 3 month period. A bi-directional link under Internet TCP-IP protocols is used for data, alarms and remote-control transmissions with the land-based data centre. Herein, we present a 29 month record for 4 parameters measured using a MAREL buoy moored in a coastal environment (Iroise Sea, Brest, France). The accuracy of the data provided by the buoy is assessed by comparison with measurements of sea water weekly sampled at the same site as part of SOMLIT (Service d'Observation du Milieu LIToral), the French network for monitoring of the coastal environment. Some particular events (impact of intensive fresh water discharges, dynamics of a fast phytoplankton bloom) are also presented, demonstrating the worth of monitoring a highly variable environment with a high frequency continuous reliable system.     

Evaluation of forest nutrition based on large-scale foliar surveys: are nutrition profiles the way of the future?

This paper introduces the use of nutrition profiles as a first step in the development of a concept that is suitable for evaluating forest nutrition on the basis of large-scale foliar surveys. Nutrition profiles of a tree or stand were defined as the nutrient status, which accounts for all element concentrations, contents and interactions between two or more elements. Therefore a nutrition profile overcomes the shortcomings associated with the commonly used concepts for evaluating forest nutrition. Nutrition profiles can be calculated by means of a neural network, i.e. a self-organizing map, and an agglomerative clustering algorithm with pruning. As an example, nutrition profiles were calculated to describe the temporal variation in the mineral composition of Scots pine and Norway spruce needles in Finland between 1987 and 2000. The temporal trends in the frequency distribution of the nutrition profiles of Scots pine indicated that, between 1987 and 2000, the N, S, P, K, Ca, Mg and Al decreased, whereas the needle mass (NM) increased or remained unchanged. As there were no temporal trends in the frequency distribution of the nutrition profiles of Norway spruce, the mineral composition of the needles of Norway spruce needles subsequently did not change. Interpretation of the (lack of) temporal trends was outside the scope of this example. However, nutrition profiles prove to be a new and better concept for the evaluation of the mineral composition of large-scale surveys only when a biological interpretation of the nutrition profiles can be provided.     

Trihalomethanes in Drinking Water of Greater Québec Region (Canada): Occurrence, Variations and Modelling

The levels of trihalomethanes (THMs) – the main species of by-product from water chlorination – were monitored in thedistribution systems of the five major drinking water utilitiesof the greater area of Québec City in order to investigate andmodel their occurrence on a spatial and seasonal basis. Data forTHMs and other water quality and operational parametersassociated with their formation were generated through a 16 monthsampling program involving several sites representing variablewater residence times, from the plant to the system extremity.The results demonstrate that the differences in measured THMlevels between the five utilities are mainly due to the variablequality of raw waters, the type of water treatment process beingused and the type and levels of applied disinfectant. Dependingon the utility, average THM levels were from 1.3 to 2.5 timeshigher in the system extremities than in the water leaving thetreatment plant. Also, average levels of THMs measured in summerat the distribution system extremities were, depending on theutility, from 2.5 to 5 times higher than the average levelsmeasured in winter. The seasonal differences were found to besignificantly greater than those observed by others in waterutilities in the United States and Europe and are explained inlarge part by the considerable changes, over the year, in thequality and temperature of surface waters in Southern Québec. Forthe five utilities under study, multivariate regression modelswere developed in order to predict spatial and seasonalvariations of THMs. Both residual chlorine demand and temperaturewere found to be better, statistically, as predictors for THMoccurrence. The usefulness of the developed models for routineand long term water quality management, as well as for assessmentof human exposure to THMs, are also discussed.     

Competitive Retention of Lead and Cadmium on an Agricultural Soil

Lead and cadmium contamination of an agricultural soil has been studied using batch and column experiments. Thermodynamics of theretention phenomena may be represented by a Langmuir isotherm foran aqueous metal concentration up to 100 mg L^-1. First order kinetics with respect to the solid phase yield good predictabilityfor both batch and column experiments. Kinetics and thermodynamics of lead retention predominate over those ofcadmium. As a consequence, lead is preferentially retainedand can even displace sorbed cadmium. In the event of anspill involving both metals, cadmium would move further inthe soil and its aqueous concentration downstream could beeven higher than that of the influent solution, increasingpotential risks. A two-region model has been used to fit all the experimental results. Satisfactory predictions for column experiments are obtained with parameters which are consistent with those obtained for the batch experiments, for which sorption is described by a Langmuir isotherm including competitive retention.     

Determination of pollution trends in an abandoned mining site by application of a multivariate statistical analysis to heavy metals fractionation using SM&T-SES

The mobility, availability and persistence of Heavy Metals (HMs), As, Cd, Cu, Ni, Pb and Zn, in contaminated soils of a former abandoned mining area were evaluated by means of a sequential extraction scheme (SES) and applying a multivariate statistical analysis to the obtained data. Chemical partitioning of HMs in each sample was determined in four fractions (acid-soluble, reducible, oxidable and residual) following the Standard Measurements and Testing (SM&T) SES, formerly BCR-SES. Statistical evaluation of results by pattern recognition techniques allowed identification of groups of samples with similar characteristics and observations of correlations between variables, determining the pollution trends and distribution of HMs within the studied area. Typical metal-fraction association and metal availability characteristics of heavy metals have been depicted. The obtained results indicate an urgent need to attenuate the hazard in that area posed by high concentrations of toxic metals, which exceed the limits specified by different European legislations on soil reclamation.     

One-year monitoring survey of organic compounds (PAHs, PCBs, TBT), heavy metals and biomarkers in blue mussels from the Arcachon Bay, France

Marine mussels Mytilus sp. were transplanted on a monthly basis in cages over one year to oyster farms and harbours in the Arcachon Bay (France) in order to assess the water quality of the bay. Contaminant levels (organotin compounds, trace metals, PCBs and PAHs) were measured in tissues of transplanted mussels and mussels from a reference station, along with physiological parameters of the mussels (condition indexes, lipid content and dry weight). Four biomarkers (AChE: acetylcholinesterase activity, GST: gluthathione S-transferase activity, CAT: catalase activity and TBARS: thiobarbituric acid-reactive substance content) were also monitored. The remote stations monitored (oyster parks) exhibited no accumulation pattern of pollutants. Their respective concentrations therefore constitute a background level of the contamination in the bay ([TBT]= 30 ng Sn g(-1) dw, [SigmaHAPs]= 100 ng g(-1) dw, [SigmaPCBs]= 35 ng g(-1) dw). The elevated chemical contamination of the largest harbour of the bay, the Arcachon harbour, can be interpreted in terms of persistence of organotin compounds ([SigmaOTs]= 1500-2000 ng Sn g(-1) dw) and PAHs ([SigmaHAPs]= 4500-5000 ng g(-1) dw) in sediments and, to a lesser extent, of direct inputs of copper ([Cu]= 20 microg g(-1) dw in harbours versus 7 in oyster parks) and petrogenic PAHs ([methylphenanthrenes]= 1600 ng g(-1) dw in the dockyard versus 170 at the gas stations), related to the use of copper-based antifouling paints and to dockyard activity, respectively. However, the Arcachon Bay presents a low contamination level by PCBs and metals, including harbour stations. Furthermore, higher levels of other PAHs (particularly alkyl PAHs such as methylphenanthrenes/1600 ng g(-1) dw) not included in the 16 PAHs from the EPA priority list (usually studied in biomonitoring programmes/1500 ng g(-1) dw) in the Arcachon harbour underline the need to integrate these compounds in biomonitoring of highly PAH-polluted areas such as harbours in order to avoid misinterpretation of the biological responses observed. Biomarker responses were not able to discriminate the different chemical contamination levels recorded in the Arcachon Bay and rather reflected changes in environmental factors. Furthermore, the strong intraspecies variability of biological responses could be due to genetic differences of mussels from the Arcachon Bay. It is the first time that such an integrated monitoring is performed in the Arcachon Bay, also taking into account seasonal variations of chemical contents and biomarkers levels in mussel tissues.     

Environmental quality control and environmental games

Conclusion  In this paper we have considered a specific environmental game emphasizing both control-prevention efforts and the propensity to pollute by a firm which adopts a given pollution abatement technology. A random payoff game was constructed and solved under a risk neutral assumption and quadratic utilities for both the firm and the environmental controller. The game thus defined, provides a wide range of interpretations and potential approaches for selecting a control-inspection policies to prevent environmental risks. There are of course many facets to this problem, which could be considered and have not been considered in sufficient depth. For example, more complex control mechanisms and liabilities, the effects of insurance and risk sharing, the application of cooperative efforts and subvention of pollution abatement investments (through tax incentives and their like), etc. have not been considered [5,7]. These are topics for further research. The basic presumption of this paper is that it is very difficult to fully enforce pollution prevention by firms, as a result, some controls are needed to ensure that firms be controlled so that appropriate efforts are carried.     

Simultaneous determination of parathion and p-nitrophenol in vegetable tissues by derivative spectrophotometry

A first derivative spectrophotometric method has been developedfor the determination of parathion and p-nitrophenol in vegetabletissues. Ethanol was used as solvent for extracting the compoundsfrom the tissues and subsequently the samples were evaluated against a vegetable tissue blank, directly by derivative spectrophotometry. The simultaneous determination of these compounds can be carried out using the zero-crossing approach for parathion at 253.0 nm and for p-nitrophenol at 273.1 nm. In the samples each analyte was determined in the presence of one another in the ranges between 4.9 to 3883.5 g g^-1 forparathion and 4.9 to 3285.3 g g^-1 for p-nitrophenol.The detection limits (3) were found to be 1.5 and 1.4 g g^-1 for parathion and p-nitrophenol, respectively. The relative standard deviations were in all instances less than1.8%. The proposed method was applied to the determination ofthe analytes in spiked leafs of corn. The results show a goodrecovery and they are in agreement with those obtained bypolarography.