An innovative statistical approach for analysing non-continuous variables in environmental monitoring: assessing temporal trends of TBT pollution

The current work presents an innovative statistical approach to model ordinal variables in environmental monitoring studies. An ordinal variable has values that can only be compared as "less", "equal" or "greater" and it is not possible to have information about the size of the difference between two particular values. The example of ordinal variable under this study is the vas deferens sequence (VDS) used in imposex (superimposition of male sexual characters onto prosobranch females) field assessment programmes for monitoring tributyltin (TBT) pollution. The statistical methodology presented here is the ordered logit regression model. It assumes that the VDS is an ordinal variable whose values match up a process of imposex development that can be considered continuous in both biological and statistical senses and can be described by a latent non-observable continuous variable. This model was applied to the case study of Nucella lapillus imposex monitoring surveys conducted in the Portuguese coast between 2003 and 2008 to evaluate the temporal evolution of TBT pollution in this country. In order to produce more reliable conclusions, the proposed model includes covariates that may influence the imposex response besides TBT (e.g. the shell size). The model also provides an analysis of the environmental risk associated to TBT pollution by estimating the probability of the occurrence of females with VDS ≥ 2 in each year, according to OSPAR criteria. We consider that the proposed application of this statistical methodology has a great potential in environmental monitoring whenever there is the need to model variables that can only be assessed through an ordinal scale of values.     

Comparing spatial and temporal changes in metal trends (Cr,Ni, Pb and Zn) on the Portuguese shelf since the 1970s

Comparison between an archive dataset, collected during the 1970s (1974–1977), and samples taken during the PALEO1 cruise (2002) enabled evaluation of large-scale and long-term spatiotemporal changes in Al, Cr, Ni, Pb and Zn contents in bulk surface sediments in four areas of the Portuguese shelf. The so-called gradient method (GM) with normalisation to Al, a proxy for terrigenous clay content, was applied. The studied areas are distributed from north to south along the western margin, with the northernmost located off shore the Ave and Douro rivers, a central one located off shore the Lis River and a southern one located off shore the Mira River. One-way ANOVA and Kruskal-Wallis tests were used to identify differences among study areas and periods of sample collection. A comparison of metal contents in 2002 samples with the Portuguese classification scheme regulation for deposition of dredged materials in coastal areas indicates good environmental quality in terms of Cr, Ni, Pb and Zn levels. Nevertheless, the GM results suggest an increase in metal loadings relative to Al from the 1970s to the 2002 samples (except for Pb). The Algarve area on the southern shelf is characterised by having high number of sites with metal level on class 2. These high values have traditionally been explained by a substantial supply of natural metals from the Guadiana, Tinto and Odiel rivers that drain areas Iberian Pyrite Belt formations. This supply has probably been magnified by present and past mining activities. For quality evaluation of marine sediments, especially when using total metal contents, this study shows the importance of considering all possible sources of metal loading. The natural grain size and composition variability have also a crucial influence on the metal content, and the combined evaluation allows a more holistic perspective.     

A temporal and spatial monitoring of organotin pollution in a harborside region of Brazil by imposex and ecological quality ratio using <Emphasis Type="Italic">Leucozonia nassa</Emphasis>

This study represents the first use of Leucozonia nassa (Mollusca-Gastropoda) in a program of long-term monitoring. Specimens of L. nassa were collected between 2006 and 2014 and analyzed for the occurrence of imposex in two areas in Southeastern Brazil, one control area and another characterized by the presence of many ports and marinas. Imposex was evaluated in nine sites based on the percentage of females exhibiting imposex (I%), relative penis length index and vas deferens sequence index, classical indices to evaluate tributyltin (TBT) impacts. Moreover, this study uses for the first time in a tropical environment the ecological quality ratio (EQR), an approach to verify the imposex levels as an indicator of the impact by organotin compounds according to the EU Water Framework Directive. The results confirm the occurrence of high levels of imposex in L. nassa with all the indices evaluated. Furthermore, the results also indicate that, despite the international ban, antifouling paints based on TBT are still possibly used in Brazil. In addition, this study shows that L. nassa has the characteristics that make it a suitable bioindicator to monitor TBT pollution, and that the use of the EQR may create important data regarding this problem.     

The use of the oyster Saccostrea glomerata as a biomonitor of trace metal contamination: intra-sample, local scale and temporal variability and its implications for biomonitoring

Cu, Cd, Zn, Pb and Se concentrations were measured in the bivalve mollusc Saccostrea glomerata(Iredale and Roughly) from two uncontaminated locations, Clyde River Estuary, Batemans Bay and Moona Moona Creek, Jervis Bay, to determine natural variability of metals associated with mass, gender, age, tissue type and site within location. Trace metals were also measured in the Clyde River Estuary over an 11 year period and in five other NSW estuaries (Hastings River, Hunter River, Georges River, Tillgerry Creek and Lake Pambula) over a 13-month period to determine temporal variability and if diploid and triploid oysters accumulate trace metals differently. There were few significant relationships between trace metal concentrations and mass and no significant differences in trace metal concentrations between female and male oysters. Younger oysters (1.3 years) had significantly higher copper concentrations and higher trace metal variability than mature oysters (3 years). Different tissues have different trace metal concentrations with muscle tissues having lower concentrations. Considerable inherent variability occurs in oyster cohorts. Analysing specific tissues did not reduce variability of trace metal concentrations. Comparison of trace metal concentrations at two sites within the Clyde Estuary showed a significant difference in zinc concentrations. Cu, Cd, Zn and Se concentrations were generally higher and less variable in triploids than diploids. Pb had a variable pattern of accumulation with no consistent elevation in diploids or triploids. Inter annual variability of trace metal concentrations was considerable and trace metal concentrations also fluctuated throughout an annual cycle with no clear seasonal trends. Measurement of trace metals at known contaminated locations showed that Saccostrea glomerata accumulates metals in response to contamination. Saccostrea glomerata meet most of the requirements to be a biomonitor of trace metal contamination as they are abundant, sessile/sedentary, easy to identify, provide sufficient tissue for analysis, and accumulate trace metals in response to contamination. However, as trace metal concentrations can vary with mass, age, estuary position, ploidy type and temporally, care must be taken to collect individual organisms of similar mass, age and ploidy type to minimise variability, and from similar consistent positions and times to allow for seasonal changes in environmental conditions. Trace metal concentration variability is higher in young animals, thus to reduce variability, older mature animals could be selected. However, with immature oysters there are no complications because of the effects of spawning i.e. sudden loss of trace metals or body mass.     

Bioindicative comparison of the fern Athyrium distentifolium for trace pollution in the Sudety and Tatra mountains of Poland

Concentrations of the elements Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn were measured in the fronds of the fern Athyrium distentifolium from the Sudety and Tatra mountains (Poland). The A. distentifolium sites in the Sudety mountains which were influenced by long-range metal transport from the former Black Triangle were distinguished by the principal component and classification analysis (PCCA). These sites were situated on the west side slopes of one of the ranges in the Sudety mountains (within a 150-km radius of the heart of the former Black Triangle) at an altitude of 700 m asl, and exposed to prevailing winds. This most affected area had significantly higher foliar concentrations of Cu, Cr and Ni which are typical for long-range transported airborne elements occurring in coal fly ash emitted by lignite combustion industry.     

Techniques and methods for the determination of haloacetic acids in potable water

Haloethanoic (haloacetic) acids (HAAs) are formed as disinfection byproducts (DBPs) during the chlorination of natural water to make it fit for consumption. Sundry analytical techniques have been applied in order to determine the concentrations of the HAAs in potable water supplies: gas chromatography (GC-MS, GC-ECD); capillary electrophoresis (CE); liquid chromatography (LC), including ion chromatography (IC); and electrospray ionization mass spectrometry (ESI-MS). Detection limits required to analyze potable water samples can be regularly achieved only by GC-ECD and ESI-MS. Without improvements in preconcentration or detector sensitivity, CE and LC will not find application to potable water supplies. The predominant GC-ECD methods use either diazomethane or acidified methanol to esterify (methylate) the carboxylic acid moiety. For HAA5 analytes, regulated under the EPA's Stage 1 DBP Rule, diazomethane is satisfactory. For HAA9 data gathered under the Information Collection Rule, acidified methanol outperforms diazomethane, which suffers from photo-promoted side reactions, especially for the brominated trihaloacetic acids. Although ESI-MS can meet sensitivity and selectivity requirements, limited instrumentation availability means this technique will not be widely used for the time being. However, ESI-MS can provide valuable confirmatory information when coupled with GC-ECD in a research setting.     

Sampling and analysis considerations for the determination of hexavalent chromium in workplace air

Airborne hexavalent chromium (Cr[VI]) is a known human respiratory carcinogen and allergen. Workers in a variety of industries may be exposed to airborne hexavalent chromium, with exposures frequently occurring via inhalation and/or dermal contact. Analytical methods for the measurement of Cr(VI) compounds in workplace samples, rather than for the determination of total elemental chromium in workplace air, are often desired because exposure limit values for Cr(VI) compounds are much lower than for total Cr. For years, sampling and analytical test methods for airborne Cr(VI) have been investigated so as to provide means for occupational exposure assessment to this highly toxic species. Inter-conversion of trivalent chromium (Cr[III]) and Cr(VI) can sometimes occur during sampling and sample preparation, and efforts to minimize unwanted redox reactions involving these chromium valences have been sought. Because of differences in toxicity, there is also interest in the ability to differentiate between water-soluble and insoluble forms of Cr(VI), and procedures that provide solubility information concerning Cr(VI) compounds have been developed. This paper reviews the state of the art concerning the measurement of airborne Cr(VI) compounds in workplace aerosols and related samples.     

An online preconcentration system for the determination of uranium in water and effluent samples

Amberlite XAD-4 resin functionalized with β-nitroso-α-naphthol was applied to an online system for the preconcentration and determination of uranium. U (VI) ions were retained on the minicolumn at an appropriate pH and then desorbed with acid solution. The amount of uranium in the eluate was measured spectrophotometrically at 650 nm using Arsenazo III as a colorimetric reagent. The limit of detection and the preconcentration factor were 1.8 μg L^???1 and 10, respectively. The chemical and flow variables affecting the preconcentration were studied. The influence of several ions on the system was also investigated. The method was successfully applied for the evaluation of uranium in water and in effluent samples.     

Spatial variability and temporal changes in the trace metal content of soils: implications for mine restoration plan

Trace metals in soils may be inherited from the parent materials or added to the system due to anthropogenic activities. In proposed mining areas, trace metals become an integral part of the soil system. Usually, researchers undertake experiments on plant species selection (for the restoration plan) only after the termination of mining activities, i.e. without any pre-mining information about the soil-plant interactions. Though not shown in studies, it is clear that several recovery plans remain unsuccessful while carrying out restoration experiments. Therefore, we hypothesize that to restore the area effectively, it is imperative to consider the pre-mining scenario of metal levels in parent material as well as the vegetation ecology of the region. With these specifics, we examined the concentrations of trace metals in parent soils at three proposed bauxite locations in the Eastern Ghats, India, and compared them at a spatio-temporal scale. Vegetation quantification and other basic soil parameters accounted for establishing the connection between soil and plants. The study recorded significant spatial heterogeneity in trace metal concentrations and the role of vegetation on metal availability. Oxidation reduction potential (ORP), pH and cation exchange capacity (CEC) directly influenced metal content, and Cu and Ni were lithogenic in origin. It implies that for effective restoration plant species varies for each geological location.     

Selection and evaluation of sequential extraction procedures for the determination of phosphorus forms in lake sediment

In order to achieve comparable measurements in the determination of phosphate forms in freshwater sediments, the Standards, Measurements and Testing Programme (formerly BCR) of the European Commission has launched a project the first step of which was to select and evaluate collaboratively existing extraction procedures. This was carried out through expert consultations and a literature survey, and was followed by the organisation of a first interlaboratory study for the evaluation of four sequential extraction schemes, one of which was selected as the most promising method for achieving comparability. This scheme, a modified version of the Williams protocol, was further tested in a second interlaboratory study. The so-called SMT extraction scheme seems promising and will provide, in the near future, a valuable tool for water managers in the field of lake restoration. It will be particularly helpful in estimating the stock of P potentially available, hence the risk of eutrophication due to internal P release.     

Interlaboratory evaluation of an extraction and fluorescence method for the determination of trace beryllium in soils

Analytical methods for the determination of trace beryllium in soils are needed so that anthropogenic sources of this element can be distinguished from native (background) levels of beryllium. In this work, a collaborative interlaboratory evaluation of a new extraction and fluorescence-based procedure for determining beryllium in soil samples was carried out to fulfil method validation requirements for ASTM International voluntary consensus standard test methods. A Canadian reference material, CCRMP Till-1 soil, with a background beryllium concentration of 2.4 microg g(-1), was selected for study. This certified reference material (CRM) was spiked and homogenized with varying levels of beryllium oxide in order to give batches of material with beryllium concentrations of 4.36 +/- 0.69, 11.5 +/- 0.7, 124 +/- 7 and 246 +/- 16 microg g(-1) (+/- values are standard deviations). In the interlaboratory study (ILS), which was carried out in accordance with an applicable ASTM International standard practice (ASTM E691), samples of these spiked soils were subjected to extraction in dilute ammonium bifluoride at approximately 90 degrees C for 40 h. Fluorescence measurement of the extracted beryllium was carried out via detection using the high quantum yield fluorophore, hydroxybenzoquinoline sulfonate (HBQS). Interlaboratory precision estimates from six participating laboratories ranged from 0.048 to 0.103 (relative standard deviations) for the five different beryllium concentrations. Pooled bias estimates resulting from this ILS were between -0.049 and 0.177 for the various beryllium levels. These figures of merit support promulgation of the analytical procedure as an ASTM International standard test method.     

A new method for the determination of trichloroacetic acid in spruce foliage and other environmental media

Trichloroacetic acid (TCAA) is a phytotoxic chemical, present throughout the environment. The majority of methods for analysis of TCAA require chemical derivatisation and multiple extraction steps prior to analysis by gas-chromatography. Here, a new analytical method for TCAA determination in environmental matrices is reported. The method is based on a modified Nielsen-Kryger steam distillation that combines into one 1 h reflux the thermal decarboxylation of TCAA to CHCl3 and the partitioning and concentration of the CHCl3 into 5 ml of hexane, which is analysed by GC. Sample preparation is minimal and no matrix standard additions are required. The background CHCl3 in the sample is removed prior to extraction by degassing the solution for 1 h with nitrogen. Optimisation of the method gave recoveries from three separate solutions of 0.31 ppb aqueous TCAA standards of 93 +/- 15% (n = 9), 110 +/- 9% (n = 9) and 105 +/- 11% (n = 6). The extraction method has been compared with a decarboxylation and headspace GC method for determination of TCAA in Sitka spruce needles. No significant difference in TCAA concentration or replicate precision between the two methods was observed.     

Development of simple and sensitive spectrophotometric method for the determination of bendiocarb in its formulations and environmental samples

Facile, selective and sensitive spectrophotometric method has been developed for the determination of bendiocarb in its insecticidal formulations, fortified water, food grains, agriculture wastewater and agriculture soil samples with prepared reagents. The method was based on alkaline hydrolysis of the bendiocarb pesticide, and the resultant hydrolysis product of bendiocarb was coupled with 2,6-dibromo-4-methylaniline to give a yellow color product with λmaxof457 nmorcouplingwith2, 6−dibromo−4−nitroanilinetoproducearedcoloredproductwithλ_max of474~nmorcouplingwith2, 4, 6−tribromoanilinetoformorangeredcoloredproducthasaλ_max of465 nm.Underoptimalconditions, Beer'slawrangefor2, 6−dibromo−4−methylaniline(DBMA)wasfoundtobe0.6−−14.0~μgmL ^-1, 0.8−−10.0 μgmL ^-1 for2, 6−dibromo−4−nitroaniline(DBNA)and0.4−−10.0 μgmL ^-1 for2, 4, 6−tribromoaniline(TBA).Themolarabsorptivityofthecolorsystemswerefoundtobe4.126~×~10⁴ lmol ^-1 cm ^-1 forDBMA, 3.254×10⁴ l~mol ^-1 cm ^-1 forDBNAand2.812×10⁴ lmol ^-1 cm ^-1 forTBA.Sandell'softhecolorreactionsare0.018 μgcm ^-2(DBMA), 0.052 μgcm ^-2(DBNA)and0.065 μgcm ^-2$ (TBA) respectively. The effect of the non-target species on the determination of bendiocarb was studied. The formation of colored derivatives with the coupling agents is instantaneous and stable for 18 h, 30 h, and 12 h. Performance of the proposed methods were compared statistically in terms Student's F and t-tests with the reported methods.     

Geochemical position of Pb,Zn and Cd in soils near the Olkusz mine/smelter,South Poland: effects of land use,type of contamination and distance from pollution source

The soils adjacent to an area of historical mining, ore processing and smelting activities reflects the historical background and a mixing of recent contamination sources. The main anthropogenic sources of metals can be connected with historical and recent mine wastes, direct atmospheric deposition from mining and smelting processes and dust particles originating from open tailings ponds. Contaminated agriculture and forest soil samples with mining and smelting related pollutants were collected at different distances from the source of emission in the Pb–Zn–Ag mining area near Olkusz, Upper Silesia to (a) compare the chemical speciation of metals in agriculture and forest soils situated at the same distance from the point source of pollution (paired sampling design), (b) to evaluate the relationship between the distance from the polluter and the retention of the metals in the soil, (c) to describe mineralogy transformation of anthropogenic soil particles in the soils, and (d) to assess the effect of deposited fly ash vs. dumped mining/smelting waste on the mobility and bioavailability of metals in the soil. Forest soils are much more affected with smelting processes than agriculture soils. However, agriculture soils suffer from the downward metal migration more than the forest soils. The maximum concentrations of Pb, Zn, and Cd were detected in a forest soil profile near the smelter and reached about 25 g kg^− 1, 20 g kg^− 1 and 200 mg kg^− 1 for Pb, Zn and Cd, respectively. The metal pollutants from smelting processes are less stable under slightly alkaline soil pH then acidic due to the metal carbonates precipitation. Metal mobility ranges in the studied forest soils are as follows: Pb > Zn ≈ Cd for relatively circum-neutral soil pH (near the smelter), Cd > Zn > Pb for acidic soils (further from the smelter). Under relatively comparable pH conditions, the main soil properties influencing metal migration are total organic carbon and cation exchange capacity. The mobilization of Pb, Zn and Cd in soils depends on the persistence of the metal-containing particles in the atmosphere; the longer the time, the more abundant the stable forms. The dumped mining/smelting waste is less risk of easily mobilizable metal forms, however, downward metal migration especially due to the periodical leaching of the waste was observed.     

Use of Sediment Quality Guidelines and pollution indicators for the assessment of heavy metal and PAH contamination in Greek surficial sea and lake sediments

Eight different surface sediment samples (K1–K8) were collected from two separate areas of Lake Koumoundourou and two samples (E1 and E2) from one area of Elefsis Bay, Athens, Greece. The level of pollution attributed to heavy metals was evaluated using several pollution indicators. Degree of Contamination, Modified Contamination Degree and Geoaccumulation Indexes were applied in order to determine and assess the anthropogenic contribution of the selected six elements (Cr, Ni, Cu, Zn, As and Pb). Moreover, the adverse effects of the sediments to aquatic organisms, from both heavy metals and polycyclic aromatic hydrocarbons (PAHs), were determined by using Sediment Quality Guidelines. The results indicated that Lake Koumoundourou is contaminated with heavy metals in a moderate degree and almost 50 % of the sediments are associated with frequent observation of adverse effects, when it comes to Ni and occasional observation of adverse effects, when it comes to Cu, Zn and Pb. As far as PAHs are concerned, around 60 % of the samples can be occasionally associated to toxic biological effects according to the effect-range classification for phenanthrene, benzo(a)anthracene, chrysene and pyrene. Finally, samples taken from the north side of the lake are more contaminated with PAHs than the ones taken from the east side probably due to the existence of the water barrier which acts as a reservoir of PAHs.     

Comparison study of five analytical methods for the fractionation and subsequent determination of aluminium in natural water samples

Five methods for aluminium fractionation used in different laboratories in Norway and Finland were compared using six control, 75 soil water and 10 lake water samples. Different fractionation principles [cation exchange, formation of the Pyrocatechol Violet (PCV) or quinolin-8-ol (oxine) complex], types of cation exchanger [Amberlite (Na/H) or Bond Elut (H)], reaction time (from 2.3 s), flow systems (flow injection analysis or segmented flow) and determination principles (molecular absorption spectrometry or ICP-AES) were tested. Determination of the 'labile' fraction was strongly dependent on the method used and the largest differences were observed between the ICP-AES method with cation exchange (Bond Elut H form) and the 'quickly reacting' method (oxine, 2.3 s). Different flow systems, both using cation exchange and determination of the PCV complex but with different reaction times and an extra acidification step, resulted in large differences in the 'reactive' and 'non-labile' fractions determined. However, the determination of the labile fraction gave similar results with both these methods. The two different types of cation exchanger used (with and without pH buffering and with different counter ions) in the ICP-AES methods resulted in differences, mainly because of a smaller 'non-labile' fraction in the non-buffered system. The two flow injection systems (oxine and PCV complexation) showed common trends, which may be connected with the short reaction times used. Comparison with theoretical equilibrium calculations using the model ALCHEMI suggested that the best correlation for the determination of the 'labile' fraction were obtained with the ICP-AES method with an Amberlite column.