Development and validation of methods for environmental monitoring of cyclophosphamide in workplaces

Methods to monitor contamination of workplaces with antineoplastic drugs have been developed and validated. Cyclophosphamide (CP) was used as a model compound as it is one of the most commonly used antineoplastic drugs. A wipe sampling method to detect contamination with CP at surfaces was developed. A personal air sampling method to sample gas and vapour on solid sorbent tubes and particles with filters was also developed. Wipe and filter samples were extracted and sorbent samples were eluted, all with ethyl acetate. The samples were analysed with liquid chromatography tandem mass spectrometry. (2)H(6)-labelled cyclophosphamide was used as an internal standard. The between-day precision was 2-5% for wipe samples, 4-6% for sorbent samples and 3-8% for filter samples. The limit of detection was 0.02 ng CP per sample for the wipe and filter methods and 0.03 ng CP per sample for the solid sorbent method. Wipe sampling on surfaces made of different materials resulted in mean recoveries between 78-106%. The desorption recovery was between 97-102% for the wipe samples, 97% for the sorbent samples and 101% for the filter samples. Samples were stable for up to 2 months at 5 degrees C and -20 degrees C and for about 2 d at room temperature. The developed methods were applied to the measurement of contamination with CP in a hospital pharmacy. Trace amounts of CP, 1.3 and 1.4 ng, were detected on surfaces in the pharmacy.     

A combination of micro-porous membrane liquid-gas extraction and solid-phase trapping for ultra trace determination of benzene in urine

A method was developed for the determination of benzene in urine. The sample was pumped through the donor channel of a membrane extraction unit with a micro-porous membrane, separating the donor channel from an identical acceptor channel purged with nitrogen. The analyte reached the acceptor channel by diffusion through the membrane and was then swept by the carrier to a solid sorbent tube, where it was trapped. The analyte was subsequently thermally desorbed and analyzed by gas chromatography (GC) with mass selective detection (MS). After optimization, the recovery was close to quantitative, or 95%. Purging the membrane unit with pure water in between the samples eliminated any memory effects. The linearity was good in the concentration range examined (20-4000 ng l(-1)), with a correlation coefficient of 0.9996. The repeatability at 50 ng l(-1) and 400 ng l(-1) was 1.4% and 1.2%, respectively. The limit of detection was 12 ng l(-1) and the limit of quantification 35 ng l(-1). This enables assessment of benzene exposures of occupationally exposed subjects, of smokers and the majority of the general population. The developed method can be easily automated.     

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.     

Concentrations and profiles of polychlorinated biphenyls, -dibenzo-p-dioxins and -dibenzofurans in livers of mink from South Carolina and Louisiana,U.S.A

In South Carolina, U.S.A., mink have been reintroduced from two apparently healthy populations to areas where populations haveexisted in the past but have been extirpated. High mortality wasobserved during transport of mink from the source populations. Inorder to elucidate the potential effects of dioxin-like compoundson the survival and reproduction of mink, concentrations of totalpolychlorinated biphenyls (PCBs), p,p-DDE, dioxin-likePCBs, polychlorinated dibenzo-p-dioxins (PCDDs), anddibenzofurans (PCDFs) were measured in livers of mink collectedfrom the source populations in South Carolina and Louisiana. Concentrations of total 2,3,7,8-tetrachlorodibenzo-p-dioxinequivalents (TEQs) for the South Carolina and Louisiana mink were21 and 14 pg g^-1, wet wt., respectively. PCB and TEQ concentrations were close to the threshold values that can, under laboratory conditions, elicit toxic effects in ranchmink. Therefore, any additional exposures of these populations toTEQs might adversely affect their populations.     

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.     

Cumulative effect assessment in Canada: a regional framework for aquatic ecosystems

Sustainable development of the aquatic environment depends upon routine and defensible cumulative effects assessment (CEA). CEA is the process of predicting the consequences of development relative to an assessment of existing environmental quality. Theoretically, it provides an on-going mechanism to evaluate if levels of development exceed the environment's assimilative capacity; i.e., its ability to sustain itself. In practice, the link between CEA and sustainable development has not been realized because CEA concepts and methods have developed along two dichotomous tracks. One track views CEA as an extension of the environmental assessment (EA) process for project developments. Under this track, stressor-based (S-B) methods have been developed where the emphasis is on local, project-related stressors, their link with aquatic indicators, and the potential for environmental effects through stressor-indicator interactions. S-B methods focus on the proposed development and prediction of project-related effects. They lack a mechanism to quantify existing aquatic quality especially at scales broader than an isolated development. This limitation results in the prediction of potential effects relative to a poorly defined baseline state. The other track views CEA as a broader, regional assessment tool where effects-based (E-B) methods specialize in quantification of existing aquatic effects over broad spatial scales. However, the predictive capabilities of E-B methods are limited because they are retrospective, i.e., the stressor causing the effect is identified after the effect has been measured. When used in isolation, S-B and E-B methods do not address CEA in the context necessary for sustainable development. However, if the strengths of these approaches were integrated into a holistic framework for CEA, an operational mechanism would exist to better monitor and assess sustainable development of our aquatic resources. This paper reviews the existing conceptual basis of CEA in Canada including existing methodologies, limitations and strengths. A conceptual framework for integrating project-based and regional-based CEA is presented.     

Investigation of the Influence of Seagrass on Fisheries Catch Level Using Isotonic Regression

The relationship between seagrass area and the commercial catch of some economically important South Australian fish species is not known in any quantitative sense. However, there is evidence in the literature to suggest that seagrass decline will detrimentally impact on species abundance and composition, and consequently that the presence or absence of seagrass will compromise the commercial and recreational fishery. In this paper we describe the construction of models based on order restricted (isotonic) regression and discuss the role of seagrass area, in terms of its influence on the level of commercial catch through modifying the effect of fishing 'effort'.     

Extractive Spectrofluorometric Determination of Quinalphos Using Fluorescein in Environmental Samples

A simple, sensitive, convenient and low cost spectrofluorometric technique for determination of quinalphos is described. Quinalphos is decomposed with sodium ethoxide. Resultant sodium diethyl thiophosphate (Na-DETP) is extracted with a cationic fluorescein as ion pair complex into 1-chloro-2-nitrobenzene. The fluorescence of the ion pair, fluorescein-DETP is measured at 530 nm after excitation at 490 nm. This technique is applicable for the determination of quinalphos in water, food grains and vegetable samples up to ng level with Amberlite XAD-4.     

Linking Land Cover and Water Quality in New York City’S Water Supply Watersheds

The Catskill/Delaware reservoirs supply 90% of New York City’s drinking water. The City has implemented a series of watershed protection measures, including land acquisition, aimed at preserving water quality in the Catskill/Delaware watersheds. The objective of this study was to examine how relationships between landscape and surface water measurements change between years. Thirty-two drainage areas delineated from surface water sample points (total nitrogen, total phosphorus, and fecal coliform bacteria concentrations) were used in step-wise regression analyses to test landscape and surface-water quality relationships. Two measurements of land use, percent agriculture and percent urban development, were positively related to water quality and consistently present in all regression models. Together these two land uses explained 25 to 75% of the regression model variation. However, the contribution of agriculture to water quality condition showed a decreasing trend with time as overall agricultural land cover decreased. Results from this study demonstrate that relationships between land cover and surface water concentrations of total nitrogen, total phosphorus, and fecal coliform bacteria counts over a large area can be evaluated using a relatively simple geographic information system method. Land managers may find this method useful for targeting resources in relation to a particular water quality concern, focusing best management efforts, and maximizing benefits to water quality with minimal costs.The United States Environmental Protection Agency through its Office of Research and Development funded and managed the research described here. It has been subjected to Agency’s administrative review and approved for publication as an EPA document.