Effects of pH on the water solubility and 1-octanol-water partition coefficient of 2,4,6-tribromophenol

2,4,6-Tribromophenol (TBP) is expected to exist in both ionic and non-ionic forms in the environment due to ionisation of the phenolic group at near neutral pH. In this study, the water solubility (Sw) and 1-octanol-water partition coefficient (Kow) of aqueous solutions of TBP at various pH values were measured using the shake flask method. The ionisation resulted in increasing Sw and decreasing Kow by two to three orders of magnitude. From the experimental results, the environmental partitioning characteristics of TBP and the effect of pH on partitioning were discussed through a comparison with the properties of tetrabromobisphenol A (TBBP-A), which has two phenolic groups. Furthermore, the pH dependence of Sw and Kow was represented using a Henderson-Hasselbalch type model and the validity of the model was evaluated. The model was found to be highly useful for predicting the pH dependence within the range of pH 3 to 9.     

Measurement of total antimony and antimony species in mine contaminated soils by ICPMS and HPLC-ICPMS

This paper describes the measurement of total antimony and antimony species in "real world" mine contaminated sediments using ICPMS and HPLC-ICPMS. Low and high temperature microwave extraction procedures (90 degrees C and 150 degrees C, respectively) using a range of nitric-hydrochloric acid combinations were examined as to their efficacy to extract antimony from six mine contaminated soils and a certified reference material. The use of the higher temperature with nitric-hydrochloric acid (1:2 (v/v)) was suitable to release antimony from sediments and the certified reference material, NIST 2710 Montana soil. Antimony concentrations obtained using this acid mixture were similar to those obtained using a more aggressive extraction with nitric, hydrochloric, perchloric and hydrofluoric acid mixture. A 25 mM citric acid solution at 90 degrees C for 15 min extracted 47-78% of antimony from soils. A Hamilton PRP X-100 anion exchange column with 20 mM EDTA mobile phase, pH 4.5, flow rate 1.5 mL min(-1) and column temperature of 50 degrees C was used to separate antimony species. Column recoveries ranged from 78-104%. The predominant form of antimony was Sb(5+). Little conversion of Sb(5+) occurred (<5%) during extraction, however, significant conversion of Sb(3+) occurred (approximately 36%). The extraction of antimony species with citric acid should be useful in the determination of inorganic antimony available to plants, as plants commonly excrete carboxylic acids, including citric acid, into their rhizospheres to mobilise trace elements for nutritional purposes.     

Laboratory and field validation of a combined NO2-SO2 Radiello passive sampler

A combined NO2-SO2 Radiello radial-type diffusive sampler was validated under controlled laboratory conditions and compared with NO2-SO2 results of 3 other type of samplers in a field comparison at two locations Ghent-Mariakerke and Borgerhout in Flanders. Laboratory exposures at different temperatures (-5, 10 and 30 degrees C) and relative humidities (0, 50 and 80% RH) in combination with varying concentration levels and exposure times were carried out, with a focus on extreme conditions. Concentration level and exposure time were changed together following suppliers linear working range of samplers and assuring absolute amounts of compounds on the sampler corresponding to those of environmental levels. The average uptake rate for NO2 for 24 hour exposures at 10 degrees C and 50% RH and tested concentration levels (+/-73, 146 and 293 ppb NO2) was 0.076 +/- 0.011 ng ppb(-1) min(-1). Uptake rates during all experiments were lower than the uptake rate given in the instruction manual of the sampler. A significant effect of temperature and relative humidity on NO2 uptake rate was observed. The temperature effect from 10 to 30 degrees C corresponds to the temperature effect given by the supplier of the samplers. High relative humidity (70 to 80%) caused a strong non-reproducible decrease of uptake rate for NO2 at 24 hour experiments but this effect was not observed at longer exposures except for the tests at -5 degrees C. At the tested temperature below zero in combination with high relative humidity the sampler showed anomalous behaviour for NO2. The possible effect of concentration level and exposure time for NO2 needs further research. The average uptake rate for SO2 calculated from all exposures is 0.478 +/- 0.075 ng of sulfate ion each ppb min of SO2 and accords to suppliers uptake rate. No clear effects of temperature, relative humidity or concentration level/exposure time on the uptake rate for SO2 were found, partly due to the large scatter of results. Although NO2 accuracy of Radiello samplers was better during field campaigns than during laboratory validation, IVL and OGAWA samplers gave better results for NO2. In the field, IVL samplers showed best agreement with the continuous analyzers for both NO2 and SO2.     

Linking groundwaters of high CO2 to aluminium levels in rivers: the case for the upper Severn in mid-Wales

Al is a critical ecotoxicant in surface waters impacted by acidic deposition. Apart from the most acidic surface waters, Al concentrations are often considered to be controlled by Al(OH)(3) or aluminosilicate (clay) solubility for modelling studies. For many UK rivers there is no clear evidence for such solubility controls even though there is the potential under moderately acidic/alkaline conditions. Here, Al solubility in ground and river water is compared for acid sensitive catchments in mid-Wales. The results reveal that there may be a solubility control within the groundwater but a more complex state of affairs within the river. The groundwater is of high CO(2) content and once in the river it degasses to raise pH. However, there is limited change in Al concentration and hence the solubility relationship is lost. The results flag the potential importance of groundwater solubility controls for Al and the potential for the groundwater zone to act as an Al filter. For positive alkalinity groundwaters, the high CO(2) levels depress the pH to near the value for minimum Al solubility. However, there is no simple groundwater end-member. Examining Al solubility controls solely within the rivers provides cryptic and misleading clues to the hydrogeological controls for Al within catchments. Assessing the within-catchment processes requires direct measurement with full consideration of both inorganic and organic attenuation.     

Trace metals solubility in rainwater: evaluation of rainwater quality at a watershed area, Istanbul

In this study, 79 bulk precipitation samples were collected at two sampling sites near Büyükçekmece Lake, one of the important drinking water sources of Istanbul, for the period of October 2001 to July 2002. The study comprised the determination of trace and toxic metals concentrations in rain water. The concentrations of the metals in this study were found to be higher than those reported by other researchers around the world. The solubility of toxic metals was found in the order of Cd > Cu > V > Zn > Ni > Pb > Cr. Solubility of metals under acidic conditions (pH < 5.5) was approximately five times higher than those under neutral conditions with Cd as the most soluble metal (50% soluble). Statistical evaluations including seasonal variations, crustal enrichment factors, and correlation matrix were discussed to identify the possible sources of these pollutants. The study revealed that anthropogenic elements were highly enriched especially for Cd > Cu > Pb which were found to be highly enriched. Significant portion of Cu and Pb could be increased by the effect of local sources like cement industry in the area; however, the rest of the investigated trace metals could be brought to the sampling site by long-range transport to the Büyükçekmece Lake watershed area.     

Occurrence of Giardia and Cryptosporidium in Italian water supplies

A total of 21 samples: raw water (RW) samples; water samples after coagulation with aluminium sulfate (clarified water: CW); and water after chlorination (treated water: TW) from a water purification plant that treats river surface water from the neighbourhood of Foggia (Italy), were analysed for the presence of Giardia cysts and Cryptosporidium oocysts. Bacteriological indicator of faecal contamination (total and faecal coliforms, faecal streptococci,), total bacterial count at 22 and 36 degrees C and physicochemical parameters (turbidity, temperature, pH) were evaluated. Cryptosporidium oocysts were not found in any samples examined, while Giardia cysts were found only in RW samples, with the maximal concentration of 8 cysts/100 l. A positive correlation was found between the Giardia densities and quality parameters such as TC, FC and TBC at 22 degrees C. Giardia levels in raw water samples correlated (p < 0.05) with TC, FC and with temperature. No other water quality parameters was consistently correlated with cysts level.     

Using Temporal Coherence to Determine the Response to Climate Change in Boreal Shield Lakes

Climate change is expected to have important impacts on aquatic ecosystems. On the Boreal Shield, mean annual air temperatures are expected to increase 2 to 4°C over the next 50 years. An important challenge is to predict how changes in climate and climate variability will impact natural systems so that sustainable management policies can be implemented. To predict responses to complex ecosystem changes associated with climate change, we used long-term biotic databases to evaluate how important elements of the biota in Boreal Shield lakes have responded to past fluctuations in climate. Our long-term records span a two decade period where there have been unusually cold years and unusually warm years. We used coherence analyses to test for regionally operating controls on climate, water temperature, pH, and plankton richness and abundance in three regions across Ontario: the Experimental Lakes Area, Sudbury, and Dorset. Inter-annual variation in air temperature was similar among regions, but there was a weak relationship among regions for precipitation. While air temperature was closely related to lake surface temperatures in each of the regions, there were weak relationships between lake surface temperature and richness or abundance of the plankton. However, inter-annual changes in lake chemistry (i.e., pH) were correlated with some biotic variables. In some lakes in Sudbury and Dorset, pH was dependent on extreme events. For example, El Nino related droughts resulted in acidification pulses in some lakes that influenced phytoplankton and zooplankton richness. These results suggest that there can be strong heterogeneity in lake ecosystem responses within and across regions.     

The effect of temperature and NaCl concentration on the kinetic method of toxicity determination using Vibrio fischeri

In this paper the effect of temperature and NaCl concentration on the kinetic method of toxicity determination using Vibrio fischeri was studied for 50 ppm Zn(2+). This work shows that both NaCl concentration and temperature affect the kinetics of toxicity as well as the luminescence of the bacteria, and hence these are important factors that need to be considered in the development of a miniaturised portable instrument. Furthermore, this work shows that the conditions for which the kinetic test was most sensitive, i.e. exhibited the greatest response, were 23 degrees C and 2% NaCl. However, at these conditions small variations in temperature and NaCl concentration could lead to great errors in the results. Thus 12.5 degrees C and 2% NaCl are preferred as at these conditions the obtained results are more robust. Although at the latter conditions the toxicity rate constant was found to be 5.5 times less than that for 23 degrees C, the value is comparable to that obtained for 15 degrees C. From the data available it was also found that the temperature dependence of the toxicity rate fits the Arrhenius equation, in a behaviour similar to that of simpler chemical reactions.     

Temperature-Electrical Conductivity Relation of Water for Environmental Monitoring and Geophysical Data Inversion

Electrical conductivity (EC) is widely used for monitoring the mixing of fresh water and saline water, separating stream hydrographs, and geophysical mapping of contaminated groundwater. The measured EC values at various temperatures need to be reported as corresponding to a standard temperature because EC is dependent on temperature. An arbitrary constant is commonly used for temperature compensation assuming that EC-temperature relation is linear (for example 2% increase of EC per 1 degrees C). This paper examines the EC-temperature relation of natural waters having vastly different compositions and salinities. EC-temperature relation was slightly nonlinear in a temperature range 0-30 degrees C, but the linear equation approximated the relation reasonably well. The temperature compensation factor corresponding to 25 degrees C ranged between 0.0175 and 0.0198. When the mean value 0.0187 was used, the error of estimating EC at 25 degrees C from EC at 10 degrees C was less than about 2% for all samples tested. Temperature compensation factors vary substantially depending on the choice of standard temperature. Therefore, a care must be taken when standard temperatures different from 25 degrees C are used.     

Leaching of potential hazardous elements of coal cleaning rejects

The geochemical characteristics of coal cleaning rejects (CCR) in Santa Catarina State, Brazil, were investigated. Around 3.5 million ton/ year of coal waste are dumped in Santa Catarina State. Coal beneficiation by froth flotation results in large amounts of CCR composed of coaly and mineral matter, the latter characterised by the occurrence of sulphide minerals and a broad array of leachable elements. The total and leachable contents of more than 60 elements were analysed. Atmospheric exposure promotes sulphide oxidation that releases substantial sulphate loads as well as Ca^2?+?, K^?+?, Mg^2?+?, Cl^??? and Al^3?+?. The metals with the most severe discharges were Zn, Cu, Mn, Co, Ni and Cd. Most trace pollutants in the CCR displayed a marked pH-dependent solubility, being immobile in near-neutral samples. The results highlight the complex interactions among mineral matter solubility, pH and the leaching of potentially hazardous elements.     

Compartment modeling of MTBE in the generic environment and estimations of the aquatic MTBE input in Germany using the EQC model

The use of the gasoline additive methyl tert-butyl ether (MTBE) has caused serious concern about groundwater and surface water contamination. The behavior of MTBE in the two most relevant compartments, surface water and air in a generic environment and in a simulated German environment is investigated using the equilibrium criterion (EQC) model. Due to lack of literature data, the half-life time of MTBE in river water is estimated to about 80-120 d (105 d) at 18 degrees C and roughly 1.5 a (year)(533 d) at 4 degrees C from a batch experiment. The EQC model considers four compartments, air, surface water, soil and sediment in an environment of typically 100,000 km2 with about 10% of the area covered with water. The user can progress through the tiered sequence of Level I to III with increasing complexity which reveals more information about the the fate of the considered chemical. The equilibrium mass distribution of MTBE calculated with the Level I model shows that 87% partitions into air and 13% into surface water at 10 degrees C. The results of the Level II calculations indicate that 50% of MTBE in the air is transported from the system and 38% in the air is degraded at 10 degrees C. The resulting total persistence time of 3 d for MTBE in the generic environment of the Level II model can be compared to the calculated value for chlorobenzene. The MTBE input into water is significantly more sensitive to the 'mode of entry' than input into air. The MTBE concentration in surface water is almost exclusively the result of direct emission into water, whereas the atmosphere can additionally be loaded by volatilization from water. The total aquatic MTBE emission in Germany and the average MTBE concentration in German surface waters were roughly estimated to 20-80 t a(-1) (tons per year)(50 t a(-1)) and 50 ng L(-1), respectively. Surface water concentrations calculated with the underlying assumptions of the model can neither be explained by exposure through waste water and industrial effluents nor with an estimated loss of industrially used MTBE in Germany. For the year-round scenario at 10 degrees C, MTBE concentrations of 19 ng L(-1) (surface water) and 167 ng m(-3) (air) result. However, it remains unclear whether the assumptions of the model, the lack of analyses from industrial effluents or both are responsible for the difference. Additional aquatic emission sources could result from gasoline transport on and storage near rivers. The comparison of winter and summer scenarios shows that in summer, atmospheric (25%) and aqueous (50%) concentrations are lower than in winter due to higher degradation rates.     

Diel Cycling of Zinc in a Stream Impacted by Acid Rock Drainage: Initial Results from a New in situ Zn Analyzer

Recent work has demonstrated that many trace metals undergo dramatic diel (24-h) cycles in near neutral pH streams with metal concentrations reproducibly changing up to 500% during the diel period (Nimick et al., 2003). To examine diel zinc cycles in streams affected by acid rock drainage, we have developed a novel instrument, the Zn-DigiScan, to continuously monitor in situ zinc concentrations in near real-time. Initial results from a 3-day deployment at Fisher Creek, Montana have demonstrated the ability of the Zn-DigiScan to record diel Zn cycling at levels below 100 μg/l. Longer deployments of this instrument could be used to examine the effects of episodic events such as rainstorms and snowmelt pulses on zinc loading in streams affected by acid rock drainage.     

Assessment of thermal stratification within stream pools as a mechanism to provide refugia for native trout in hot, arid rangelands

Native trout species, such as the redband trout (Oncorhynchus mykiss), occupy thermally harsh stream habitats in hot, arid rangeland basins of the western United States. Declines in the distribution and abundance of these species has generated interest in understanding how these cold water species survive in these systems, as well as in identifying opportunities to restore these species to their former ranges. The purpose of this study was to assess the potential for thermal stratification to provide thermal refuge for redband trout in stream pools characterized by warm intermittent flow conditions on arid rangelands. We studied vertical thermal stratification in two pools during three summers on Boles Creek located on the Modoc Plateau in extreme northeastern California. Water and air temperature data were collected on a 0.5 h time step from 15-Jun through 15-Sep during 1996, 1997, and 2000 using commercial temperature data-loggers. Water temperature was measured at the top (0.3 m below pool surface) and bottom (0.3 m above pool substrates) of each pool. Vertical thermal stratification occurred within these pools creating conditions as much as 7.6 ˚C cooler and consistently more constant at the bottom of pools compared to pool surface waters. Thermal stratification was dependent upon air temperature with the magnitude of stratification increasing as air temperature increased. The magnitude of thermal stratification varied significantly from year to year, likely reflecting variation in annual weather conditions. The thermal regime in the study pools was often near the upper lethal limit reported for redband trout, but temperatures at the bottom of these pools did offer refuge from lethal temperatures realized near the pool surface. Temperatures at pool bottom were consistently above optimal levels published for redbands.     

Effects of temperature parameters on thermal-optical analysis of organic and elemental carbon in aerosol

Thermal-optical analysis (TOA) is a popular method to determine aerosol elemental carbon (EC) and organic carbon (OC) collected on quartz fiber filter. However, temperature protocol adopted in TOA has great effects on OC and EC results. The purpose of this study is to investigate and quantify the effects of maximum temperature (T(max)) and residence time (RT) for each step in helium stage on ECOC measurements. Fourteen typical source samples and 20 ambient samples were collected and six temperature programs were designed for this study. It was found that EC value decreases regularly as T(max ) ascends, i.e., EC results from T(max) of 650 degrees C, 750 degrees C and 850 degrees C are 0.89 +/- 0.06, 0.76 +/- 0.10, 0.62 +/- 0.13 times EC value from T( max) of 550 degrees C, respectively, and the magnitude of EC drop (EC(d), percent) is significantly correlated with OC abundance in total carbon (R(OC/TC)), expressed as EC(d) = 66.8R(OC/TC)-14.4 (r = 0.87); pyrolized OC(POC) values are also sensitive to T(max), but there are various trends for samples with different OC constituents. On average of the samples studied here, prolonged RT reduces EC values by only 3%, almost negligible compared to the effect of T(max), and reduces POC by 9%, much less than that by previous report.     

Optimizing the removal of carbon phases in soils and sediments for sequential chemical extractions by coulometry

We have developed a coulometric technique to optimize the removal of the carbonate and organic fractions for sequential chemical extractions of soils and sediments. The coulometric system facilitates optimizing these two fractions by direct real-time measurement of carbon dioxide (CO2) evolved during the removal of these two fractions. Further analyses by ICP-MS and alpha-spectrometry aided in interpreting the results of coulometry experiments. The effects of time, temperature, ionic strength and pH were investigated. The sensitivity of the coulometric reaction vessel/detection system was sufficient even at very low total carbon content (< 0.1 mol kg-1). The efficiency of the system is estimated to be 96% with a standard deviation of 8%. Experiments were carried out using NIST Standard Reference Materials 4357 Ocean Sediment (OS), 2704 Buffalo River Sediment (BRS), and pure calcium carbonate. Carbonate minerals were dissolved selectively using an ammonium acetate-acetic acid buffer. Organic matter was then oxidized to CO2 using hydrogen peroxide (H2O2) in nitric acid. The carbonate fraction was completely dissolved within 120 min under all conditions examined (literature suggests up to 8 h). For the OS standard, the oxidation of organic matter self-perpetuates between 45 and 50 degrees C, a factor of two less than commonly suggested, while organic carbon in the BRS standard required 80 degrees C for the reaction to proceed to completion. For complete oxidation of organic matter, we find that at least three additions of H2O2 are required (popular methods suggest one or two).     

Carbonate induced dissolution of uranium containing precipitates under cement leachate conditions

The effects of carbonate on uranium (VI) solubility under aerobic and cementitious conditions have been investigated. The information is of relevance to low level nuclear waste disposal. Aqueous NaOH, KOH, Ca(OH)2 and a cement leachate solution were added to uranyl nitrate solution. Afterwards, increasing amounts of ammonium carbonate were added to re-dissolve the precipitates. The precipitates were characterised by means of X-ray powder diffraction (XRPD) measurements and modelling studies. The model calculations were performed using the MINTEQA2 speciation code, with an expanded database incorporating uranium stability constants taken from the HATCHES database. The measured and predicted amounts of CO3(2-) needed to dissolve the precipitates were compared. The knowledge gained from the 'pure' systems was used to rationalise the precipitation and re-dissolution behaviour observed in the leachate system. The lack of uranium solubility at low carbonate levels brought into question literature formation constants for UO2(OH)3- and UO2(OH)4(2-). An approximate log K value of 26.8 for K2U2O7 formation was estimated from the KOH results at pH 12. Generally, uranium solubilities are expected to be insignificant at low level nuclear waste sites because anaerobic conditions should persist. However, this study has demonstrated that solubility in leachate could rise at high pH and high carbonate levels, if aerobic conditions were to develop. Soluble U(VI) species would be formed. The novel part of the study has been to reproduce the effects and to correlate enhanced solubilities with model predictions. Consequently, the study has re-emphasised the need for appropriate environmental monitoring of such sites.     

A novel in vitro exposure technique for toxicity testing of selected volatile organic compounds

Exposure to vapours of volatile chemicals is a major occupational and environmental health concern. Toxicity testing of volatile organic compounds (VOCs) has always faced significant technological problems due to their high volatility and/or low solubility. The aim of this study was to develop a practical and reproducible in vitro exposure technique for toxicity testing of VOCs. Standard test atmospheres of xylene and toluene were generated in glass chambers using a static method. Human cells including: A549-lung derived cell lines, HepG2-liver derived cell lines and skin fibroblasts, were grown in porous membranes and exposed to various airborne concentrations of selected VOCs directly at the air/liquid interface for 1 h at 37 degrees C. Cytotoxicity of test chemicals was investigated using the MTS (3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium) and NRU (neutral red uptake) assays following 24 h incubation. Airborne IC(50) (50% inhibitory concentration) values were determined using dose response curves for xylene (IC(50)=5350+/- 328 ppm, NRU; IC(50)=5750+/- 433 ppm, MTS in skin fibroblast) and toluene (IC(50)=0 500+/- 527 ppm, NRU; IC(50)=11,200 +/- 1,044 ppm, MTS in skin fibroblast). Our findings suggest that static direct exposure at the air/liquid interface is a practical and reproducible technique for toxicity testing of VOCs. Further, this technique can be used for inhalational and dermal toxicity studies of volatile chemicals in vitro as the exposure pattern in vivo is closely simulated by this method.     

Two thousand years of atmospheric rare earth element (REE) deposition as revealed by an ombrotrophic peat bog profile,Jura Mountains,Switzerland

A peat core from a Swiss bog represents 2110 14C years of peat accumulation and provides a continuous record of atmospheric rare earth element (REE) deposition. This is the first study providing a time-series of all REE originating from the atmosphere. Concentrations of the 14 REE (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) were determined using inductively coupled plasma-mass spectrometry (ICP-MS) after dissolution of 200 mg aliquots of age-dated peat samples with 3 ml HNO3 and 0.1 ml HBF4 at 240 degrees C in a microwave autoclave. Strict quality control schemes were applied to ensure the accuracy of the applied analytical methodology. Previous analyses of selected REE by instrumental neutron activation analysis (INAA) in the same set of peat samples revealed that INAA frequently under- or overestimated REE concentrations in a systematic manner. Concentration profiles obtained for all REE were almost identical, except for Ce and Eu. Calculation of enrichment factors (EF) revealed a distinct depletion of heavy REE relative to light REE in peat samples since the beginning of the 19th century which marks the onset of the Industrial Revolution in Europe, suggesting a pronounced influence by anthropogenic activities. Enrichments of REE calculated using Sc as a reference element exceeded unity, relative to the Upper Continental Crust. Overall, EF in all peat samples ranged from 1.96 for Sm to 2.34 for Gd, with considerably lower EF for Ce (1.82) and Eu (1.44), respectively. A significant enrichment of all REE which may have been caused by military activities, was observed in the peat sample dating from World War II (1944); this exceptional sample, however, is not enriched in Ce. The concentration profiles of REE were similar but not identical to those of other lithogenic, conservative reference elements such as Sc, Y, Al, Zr and Ti. While it has been suggested that individual REE concentrations or the sum of REE can be used as a reference parameter to calculate crustal EF in environmental samples the data presented here indicates that anthropogenic emissions of REE cannot simply be ignored.     

Concentrations of sulphur and heavy metals in needles and rooting soils of Masson pine (Pinus massoniana L.) trees growing along an urban–rural gradient in Guangzhou, China

Current (C) and previous year (C + 1) needles and soils (organic horizon, 0-10 cm and 10-20 cm mineral depth) of Masson pine (Pinus massoniana L.) trees were sampled at four forested sites (Huang Pu industrial district, HP; South China Botanical Garden, BG; Mao Feng Mt., MF; and Nan Kun Mt., NK) in Guangzhou along a urban-rural gradient and analyzed for sulfur (S) and heavy metals (Cu, Zn, Ni, Cd, Cr and Pb) concentrations. Needle concentrations of all the elements were significantly higher at industrial HP than at other three sites, except for Cu and Pb which were highest at the traffic site (BG). The C + 1 needles generally had higher Cu, Cd, Pb, Zn, Cr than the C needles while the opposite was for Ni and S. Total and available Cd, Pb, Zn in soils peaked at the urban sites (HP and BG) and decreased at suburban MF and rural NK. Heavy metals were generally higher in the organic soils than in the mineral soils at all sites. Zinc and Pb at all sites, and Cd, S and Cu at the urban sites (HP and BG) in soils or pine needles were above or near their respective natural background levels, implying that threats resulted from these toxic elements occurred on local particularly urban forests, but did not for Cr and Ni due to their presence below their background values. Our results demonstrated that elements concentrations in needles and soils had reflected the variability of pollutants and the environmental quality change along the urban-rural transect, and were efficient as biomonitors to assess the influence of anthropogenic activities along the urbanization course on forest health.     

Stability and storage problems in organotin speciation in environmental samples

The stability of both tributyltin (TBT) and triphenyltin (TPT) in water, sediment, oysters and cockles was studied over a period of 18 months using several storage conditions. Butyltins were stable in unacidified sea-water stored in polycarbonate bottles in the dark at 4 degrees C for 7 months, but half of the TBT concentration was lost after 540 d. A comparable preservation time was achieved for butyltins stored on C18 cartridges at room temperature. However, phenyltins extracted from sea-water were stable for only 60 d stored on cartridges and even more pronounced losses (about 90% after 540 d) occurred when they were stored in either polycarbonate or Pyrex glass bottles. Losses of organotins were observed in sediments after air drying and pasteurization treatments using a freeze-dried sediment as a comparator, whereas both butyltin and phenyltin species remained stable in sediments stored at -20 degrees C for the 18 months tested, irrespective of the treatment used for stabilization. Air drying followed by pasteurization was shown to be superior to other treatments for the stabilization of organotin compounds in sediments stored at higher temperatures, but 30% of TBT was lost after 540 d at 25 degrees C. Finally, butyltins were stable in both frozen cockles and oysters in the dark over a 7 month period and in freeze-dried samples stored at 4 degrees C for 5 months, but TBT losses of about 70% were observed after 540 d.