Effects of field storage method on <Emphasis Type="Italic">E. coli</Emphasis> concentrations measured in storm water runoff

Storm water runoff is increasingly assessed for fecal indicator organisms (e.g., Escherichia coli, E. coli) and its impact on contact recreation. Concurrently, use of autosamplers along with logistic, economic, technical, and personnel barriers is challenging conventional protocols for sample holding times and storage conditions in the field. A common holding time limit for E. coli is 8 h with a 10 °C storage temperature, but several research studies support longer hold time thresholds. The use of autosamplers to collect E. coli water samples has received little field research attention; thus, this study was implemented to compare refrigerated and unrefrigerated autosamplers and evaluate potential E. coli concentration differences due to field storage temperature (storms with holding times ≤24 h) and due to field storage time and temperature (storms >24 h). Data from 85 runoff events on four diverse watersheds showed that field storage times and temperatures had minor effects on mean and median E. coli concentrations. Graphs and error values did, however, indicate a weak tendency for higher concentrations in the refrigerated samplers, but it is unknown to what extent differing die-off and/or regrowth rates, heterogeneity in concentrations within samples, and laboratory analysis uncertainty contributed to the results. The minimal differences in measured E. coli concentrations cast doubt on the need for utilizing the rigid conventional protocols for field holding time and storage temperature. This is not to say that proper quality assurance and quality control is not important but to emphasize the need to consider the balance between data quality and practical constraints related to logistics, funding, travel time, and autosampler use in storm water studies.     

Evaluation of preservation methods for nutrient species collected by automatic samplers

Automatic samplers are a common method of data collection for numerous monitoring projects in the South Florida region and elsewhere. Although total phosphorus (TP) is the primary parameter of interest within this region, nitrogen species such as ammonia nitrogen (NH₄-N), nitrate+nitrite nitrogen (NO_x-N), and total kjeldahl nitrogen (TKN) are also collected and analyzed. Federal and state quality assurance guidelines require nutrient samples to be preserved by acidification with H₂SO₄ to a pH < 2 and stored immediately at 4 °C. However, the remoteness of manysampling locations in South Florida makes it difficult to supplyelectricity for the refrigeration of samples collected by autosamplers. In addition, the use of propane-powered refrigerated autosamplers is a costly and ineffective solution in the South Florida climate. Consequently, while samples collected at these remote locations are routinely pre-preservedwith acid, they are not cooled to 4 °C for a period fromone to seven days. This study evaluated if a statistically significant difference ( = 0.05) existed between concentrations of nitrogen species from a common source samplethat was either: processed immediately; refrigerated to 4 °C for seven days; or not refrigerated for seven days.In all cases, the collected sample was pre-preserved by adding 1 mL of 50% H₂SO₄ to each 1 L discrete sample container before each 7 day testing period. Differences in concentrations of the calculated parameter total nitrogen (TN)were also investigated.Analyses using the Wilcoxon Signed-Rank Test showed no significant differences among the three treatment groups for NO_x-N, TKN, TN and TP. Significant differences were observedwhen the NH₄-N samples that were processed immediately werepaired with NH₄-N samples that were left unrefrigerated or refrigerated for seven days. Information from this study can be used by researchers and managers in evaluating the usefulness of nutrient water quality data that is collected when sample refrigeration is not available.     

Field cryofocussing hydride generation applied to the simultaneous multi-elemental determination of alkyl-metal(loid) species in natural waters using ICP-MS detection

Two hydride generation manifold systems, utilizing flow injection and cryotrapping techniques for alkyl-metal(loid) speciation analysis in natural waters, are described in this paper. They provide shipboard capacity for simultaneous derivatization of analytes with NaBH4 and cryotrapping of the generated products in a field packed column at -196 degrees C. The first system is a large-volume hydride generator, using a reagent-injection flow technique as a flow batch type, that has been fully optimized and applied to the simultaneous detection of alkylated species in estuarine waters. The technique permits the analysis of a large volume sample (0.5-11) at a sampling rate of 3 h-1. The second is an online continuous flow hydride generator. A sampling rate of 3-12 h-1 can be achieved with samples of 0.1-0.51. In addition, shipboard operation eliminates major problems related to sample pretreatment, transport and storage. Ultra-trace multi-element determination is finally performed in the laboratory by cryogenic GC hyphenated with ICP-MS. Routine detection limits of 0.5-10 pg (as metal) for 0.51 water samples were achieved for the selected alkyl-metal(loid) species of arsenic, germanium, mercury and tin. Concentrations of various species, obtained from water samples taken from the Rhine estuary, are also presented. These species include alkylated arsenic compounds, other than methyl derivatives, that have been tentatively identified and are reported here for the first time.     

Changes in the heavy metal and nutrient contents of dried feather mosses during long-term storage

This study measured heavy metal and nutrient concentrations of two feather mosses during the periods of dry storage. Samples (Hylocomium splendens, Pleurozium schreberi) were collected in the nationwide moss surveys carried out on the permanent sample plots of the 8th Finnish National Forest Inventory in 1985–86, 1990, 1995 and 2000. A small amount of each moss sample was analyzed soon after collection, and the remainder was dried and stored at the Paljakka environmental specimen bank (ESB). The 108 stored samples from 27 plots were reanalyzed in 2008. Concentrations of heavy metals (Cd, Cr, Cu, Fe, Ni, Pb, Zn) and nutrients (Ca, K, Mg, P) were determined and compared for each survey year. Overall, Fe, Pb and Cr concentrations decreased, and Cu concentrations increased significantly during storage. The greatest decrease was observed in samples from plots where their initial concentrations were the highest. Changes in the concentrations of Cd, Ni and Zn were less pronounced. The loss of heavy metals is likely due to drying when cell membranes rupture and some of the surface material is lost. K, P and, to some extent, Mg concentrations increased during storage, whereas Ca did not change significantly. Nutrient increase is probably due to their movement from older to younger growths during the initial phase of drying. Ca is mostly bound to cell walls and is not easily released. Results emphasize the importance of establishing the intended use of a stored moss prior to sampling, in order to select and optimize an appropriate storage technique.     

Chromium redox speciation in natural waters

Dissolved hexavalent chromium concentrations were determined in river, estuarine and coastal waters of the Humber catchment in north-east England. Samples were collected, filtered, extracted on site and after storage for up to eight days. Hexavalent chromium concentrations did not change by more than 0.05 microg l(-1) (not significant, p = 0.05) over this period. Total chromium concentrations in the catchment were less than 1.0 microg l(-1). This is low in relation to the proposed Environmental Quality Standard. Hexavalent chromium accounted for between 27% and 100% of the total dissolved concentration, with an average of approximately 50%. The proportion of Cr(III) and Cr(VI) in the rivers and estuary were of the same range as previously measured in 1993. The addition of Cr(III) and Cr(VI) to fresh and saline water samples illustrates the complexity of the factors controlling chromium speciation in natural waters. The presence of oxidisable organic matter and the stabilising role of complexing organic ligands are proposed as the main controlling influences of redox speciation in filtered samples.     

Sampling and analyses of colloids at the Drigg low level radioactive waste disposal site

Water samples have been extracted from inside (from standpipes) and from outside (from boreholes) of the trenches at the low level radioactive waste disposal site at Drigg in Cumbria, UK. The samples were taken anaerobically from between 8.5 and 10.0 m below the surface using a submersible pump at low flow rates to ensure that the waters in the standpipes and boreholes were maintained at constant levels. To ensure representative samples, the Eh, pH. conductivity, temperature, iron and dissolved oxygen concentrations of the waters were taken during initial purging and during sampling. The gross tritium, gross non-tritium beta, gross alpha and gamma activities of each sample were determined using suitable sample preparation and counting techniques. Samples were then anaerobically, sequentially filtered through 12 microm, 1 microm, 30 kDa and 500 Da filter membranes. The filtrates were analysed for gross alpha, gross non-tritium beta and gamma activities. SEM and STEM analyses were used to determine the colloid population. An energy dispersive analyser on the SEM was used to determine the major elements present in the colloids. UV-visible spectrophotometry, fluorescence spectrophotometry and high performance size exclusion liquid chromatography were used to analyse the waters before and after treatment with ion exchange materials to determine whether natural organic matter was present in the waters. Results showed that two major types of colloids (iron containing colloids and silicon containing colloids) were present in the waters. There were also a small number of other colloids that contain, as major elements, aluminium, calcium and chromium. Organic colloids were also present. The majority of the radioactivity in the waters was due to tritium. Waters taken from outside the trenches contained low levels of non-tritium beta activities and alpha activities which were lower than the minimum detectable amount. Waters taken from the trenches contained non-tritium beta activities and low levels of alpha emitters. Filtration of the trench waters showed that some of the alpha activity was retained by the 30 kDa and 500 Da membranes suggesting that this activity was associated with small colloids. Radioactivity was not found to be associated with colloids present in the waters taken from outside the trenches. Possible reasons for this observation could be that radionuclide bearing colloids have not yet reached the far-field or that the radionuclide concentration is diluted to below the minimum detectable amount. After concentrating two of the samples by factors of x20 and x 16 respectively, 2.4+/-0.1 and 0.6+/-0.1 Bq dm(-3) of 137Cs were measured.     

碱化保存淡水及海水样品测定甲基汞和总汞

本文研究了水样保存条件对汞分析物稳定性的影响。常规总汞分析酸化水样保存法只适用于保存寒冷冬季水样测定甲基汞,而夏季水样在酸化保存过程中甲基汞会转化为无机汞。碱化（ｐＨ＞１２）保存天然水样可以防止甲基汞无机化,并且同时适用于长期室温保存冬季和夏季水样测定甲基汞和总汞。聚氟塑料瓶、聚丙烯塑料瓶、聚乙烯塑料瓶和硼玻璃瓶均可用于保存碱化水样测定甲基汞,但只有前两种容器同时适用于总汞分析水样保存。本文认为天然水样中的微生物是水样保存过程中导致甲基汞无机化的主要因素。     

Effect of domestic storage tanks on the quality of drinking waters

An investigation covering 12 districts of Baghdad city was conducted over 2 yr to monitor the effect of domestic storage practice on the quality of drinking water. Water storage tanks are widely used in Iraq as an additional water source. Tap and stored waters were tested for their chemical constituents i.e. Ca, Mg, Na, K, Cl, Zn, Fe, Pb, Cd, and total hardness (T.H.). All the tested elements were within the permissible limits. However, statistical analysis showed a significant variation between the different districts for T.H., Cu, Mg and chloride for both tap and stored waters. Seasonal variations have a significant effect on the levels of some elements. The quality of stored water was not affected by storage practice. Zinc, Pb and Fe were the only elements that showed some variation in the stored waters. This was attributed to the effects of corrosion of the tank metal and the migration of metals from the distribution system.     

A comparison of sampling and analysis methods for low-ppbC levels of volatile organic compounds in ambient air

A carefully designed study was conducted during the summer of 1998 to collect samples of ambient air by canisters and compare the analysis results to direct sorbent preconcentration results taken at the time of sample collection. Thirty-two 1 h sample sets were taken, each composed of a "near-real-time" sample analyzed by an autoGC-MS XonTech 930/Varian Saturn 2000 system, and Summa and Silco canisters. Hourly total non-methane organic carbon (TNMOC), ozone, and meteorological measurements were also made. Each canister was analyzed on the autoGC-MS system for a target list of 108 volatile organic compounds (VOCs) and on a manual cryosampling GC-FID system. Comparisons were made between the collection and analysis methods. Because of the low sample loading (150-250 ppbC TNMOC), these comparisons were a stringent test of sample collection and analysis capabilities. The following specific conclusions may be drawn from this study. Reasonable precision (within 15% mean difference of duplicate analyses from the same canister) can be obtained for analyses of target VOCs at low-ppbC concentrations. Relative accuracy between the GC-MS and GC-FID analysis methods is excellent, as demonstrated by comparisons of analyses of the same canisters, if measurements are sufficiently above the detection limits. This is especially significant as the GC-MS and GC-FID were independently calibrated. While statistically significant differences may be observed between the results from canister and near-real-time samples, the differences were generally small and there were clear correlations between the canister results and the near-real-time results. Canister cleanliness limits detection below the EPA Method TO-14 acceptance standard of 0.2 ppbv (0.2-2 ppbC for target analytes).     

The efficacy of protoporphyrin as a predictive biomarker for lead exposure in canvasback ducks: Effect of sample storage time

We used 363 blood samples collected from wild canvasback dueks (Aythya valisineria) at Catahoula Lake, Louisiana, U.S.A. to evaluate the effect of sample storage time on the efficacy of erythrocytic protoporphyrin as an indicator of lead exposure. The protoporphyrin concentration of each sample was determined by hematofluorometry within 5 min of blood collection and after refrigeration at 4 °C for 24 and 48 h. All samples were analyzed for lead by atomic absorption spectrophotometry. Based on a blood lead concentration of 0.2 ppm wet weight as positive evidence for lead exposure, the protoporphyrin technique resulted in overall error rates of 29%, 20%, and 19% and false negative error rates of 47%, 29% and 25% when hematofluorometric determinations were made on blood at 5 min, 24 h, and 48 h, respectively. False positive error rates were less than 10% for all three measurement times. The accuracy of the 24-h erythrocytic protoporphyrin classification of blood samples as positive or negative for lead exposure was significantly greater than the 5-min classification, but no improvement in accuracy was gained when samples were tested at 48 h. The false negative errors were probably due, at least in part, to the lag time between lead exposure and the increase of blood protoporphyrin concentrations. False negatives resulted in an underestimation of the true number of canvasbacks exposed to lead, indicating that hematofluorometry provides a conservative estimate of lead exposure.The U.S. Government's right to retain a non-exclusive, royalty-free licence in and to any copyright is acknowledgedDeceased     

Impact of wastewater treatment plant discharge of lidocaine, tramadol, venlafaxine and their metabolites on the quality of surface waters and groundwater

The presence of the anesthetic lidocaine (LDC), the analgesic tramadol (TRA), the antidepressant venlafaxine (VEN) and the metabolites O-desmethyltramadol (ODT) and O-desmethylvenlafaxine (ODV) was investigated in wastewater treatment plant (WWTP) effluents, in surface waters and in groundwater. The analytes were detected in all effluent samples and in only 64% of the surface water samples. The mean concentrations of the analytes in effluent samples from WWTPs with wastewater from only households and hospitals were 107 (LDC), 757 (TRA), 122 (ODT), 160 (VEN) and 637 ng L(-1) (ODV), while the mean concentrations in effluents from WWTPs treating additionally wastewater from pharmaceutical industries as indirect dischargers were for some pharmaceuticals clearly higher. WWTP effluents were identified as important sources of the analyzed pharmaceuticals and their metabolites in surface waters. The concentrations of the compounds found in surface waters ranged from 相似文献   

Comparison of precipitation chemistry measurements obtained by the Canadian Air and Precipitation Monitoring Network and National Atmospheric Deposition Program for the period 1995–2004

Precipitation chemistry and depth measurements obtained by the Canadian Air and Precipitation Monitoring Network (CAPMoN) and the US National Atmospheric Deposition Program/National Trends Network (NADP/NTN) were compared for the 10-year period 1995–2004. Colocated sets of CAPMoN and NADP instrumentation, consisting of precipitation collectors and rain gages, were operated simultaneously per standard protocols for each network at Sutton, Ontario and Frelighsburg, Ontario, Canada and at State College, PA, USA. CAPMoN samples were collected daily, and NADP samples were collected weekly, and samples were analyzed exclusively by each network’s laboratory for pH, H^?+?, Ca^2?+?, Mg^2?+?, Na^?+?, K^?+?, $\text{NH}_{4}^{+}$ , Cl^???, $\text{NO}_{3}^{-}$ , and $\text{SO}_{4}^{2-}$ . Weekly and annual precipitation-weighted mean concentrations for each network were compared. This study is a follow-up to an earlier internetwork comparison for the period 1986–1993, published by Alain Sirois, Robert Vet, and Dennis Lamb in 2000. Median weekly internetwork differences for 1995–2004 data were the same to slightly lower than for data for the previous study period (1986–1993) for all analytes except $\text{NO}_{3}^{-}$ , $\text{SO}_{4}^{2-}$ , and sample depth. A 1994 NADP sampling protocol change and a 1998 change in the types of filters used to process NADP samples reversed the previously identified negative bias in NADP data for hydrogen-ion and sodium concentrations. Statistically significant biases (α = 0.10) for sodium and hydrogen-ion concentrations observed in the 1986–1993 data were not significant for 1995–2004. Weekly CAPMoN measurements generally are higher than weekly NADP measurements due to differences in sample filtration and field instrumentation, not sample evaporation, contamination, or analytical laboratory differences.     

Comparison of bioassessment results and costs between preserved and unpreserved macroinvertebrate samples from streams

The choice to use or not use a preservative before sorting macroinvertebrate samples (i.e., dead specimens vs. living specimens) is based on studies not solely focused on the effects of preservation. Using identical sample processing protocols, we compared preserved and unpreserved samples for the following parameters: (1) the number of taxa and individuals for each major macroinvertebrate group, (2) ecological quality classes calculated with a multimetric index developed for the assessment of small Dutch lowland streams, and (3) costs of sample processing. We collected macroinvertebrate samples from three lowland streams in the Netherlands. At each site, we collected six replicate samples, of which three samples were preserved and three were not. Significantly different numbers of Ephemeroptera individuals and Hydracarina taxa and individuals were collected from preserved samples compared to unpreserved samples. In assessments based on these individual metrics, standardization of sample processing will be required. In streams with Ephemeroptera, the preservation of samples is necessary to optimize the number of Ephemeroptera individuals collected. In streams that contain Hydracarina, the preservation of samples will result in an underestimation of the number of Hydracarina taxa and individuals present. In only one instance there was a difference in ecological quality between preserved and unpreserved samples, indicating that assessing small Dutch lowland streams does not require standardization of sample preservation as part of the sample processing protocol. We detected no significant differences in sample processing costs between preserved and unpreserved samples.     

Bias from two analytical laboratories involved in a long-term air monitoring program measuring organic pollutants in the Arctic: a quality assurance/quality control assessment

Initiated in 1992, air monitoring of organic pollutants in the Canadian Arctic provided spatial and temporal trends in support of Canada's participation in the Stockholm Convention of Persistent Organic Pollutants. The specific analytical laboratory charged with this task was changed in 2002 while field sampling protocols remained unchanged. Three rounds of intensive comparison studies were conducted in 2004, 2005, and 2008 to assess data comparability between the two laboratories. Analysis was compared for organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) in standards, blind samples of mixed standards and extracts of real air samples. Good measurement accuracy was achieved for both laboratories when standards were analyzed. Variation of measurement accuracy over time was found for some OCPs and PCBs in standards on a random and non-systematic manner. Relatively low accuracy in analyzing blind samples was likely related to the process of sample purification. Inter-laboratory measurement differences for standards (<30%) and samples (<70%) were generally less than or comparable to those reported in a previous inter-laboratory study with 21 participating laboratories. Regression analysis showed inconsistent data comparability between the two laboratories during the initial stages of the study. These inter-laboratory differences can complicate abilities to discern long-term trends of pollutants in a given sampling site. It is advisable to maintain long-term measurements with minimal changes in sample analysis.     

Flow-injection analysis with fluorescence detection for the determination of trace levels of ammonium in seawater

A method using flow-injection, gas-diffusion, derivatisation and then fluorescent detection has been established for ammonium ion determination in seawater. The fluorescent derivative formed by reacting ortho-phthaldialdehyde (OPA) and sulfite with ammonia gives high sensitivity while removing potential interferences. This is required to measure the low concentrations of ammonium often seen in the open ocean. The experimental conditions (flow-rate, reagent concentrations, membrane configurations, etc.) were manipulated to improve performance. For a sample throughput of 30 samples h(-1), the limit of detection was 7 nM, the coefficient of variation was 5.7% at 800 nM, and the calibration curve was linear to at least 4 micromol L(-1). Interferences were minimised by a gaseous diffusion step. Volatile small molecular-weight amines as interferents were discriminated against by this method. They neither passed through the membrane as efficiently as ammonia, nor reacted as readily with OPA when sulfite was the reductant. Contamination by ammonia from laboratory and shipboard sources complicates application of the method to natural waters, especially measurement of low concentrations (<100 nM) in open-ocean waters. Steps to overcome contamination are described in detail. Some results are presented for ammonium determination in Southern Ocean and Huon Estuary (Tasmania) waters.     

气相分子吸收光谱法测定海水中的氨氮

采用气相分子吸收光谱法测定海水中的氨氮,并对相关影响因素进行探讨。结果证实,近海岸海水和河口水样品加酸固定后需调节pH值至中性;无须滤膜抽滤,可直接上机检测;所用溴酸盐混合储备液和40%氢氧化钠溶液在25℃保存不宜超过2周,超过25℃应现用现配;采集好的水样不宜长时间保存,应立即测定。方法在ρ(氨氮)为0.01~0.40 mg/L和0.10~2.00 mg/L范围内均具有良好的线性,r值均0.999;方法检出限为0.003 mg/L;实际样品和标准样品的RSD为1.0%~1.6%;加标回收率为94.0%~110%。与次溴酸盐氧化法相比,二者氨氮的测定结果无显著性差异,气相分子吸收光谱法测定氨氮的范围更宽,高浓度的氨氮样品可直接检测,减少稀释带来的误差。     

Characterizing Small Subbasins: A Case Study from Coastal Oregon

A fine-grained statisticaly robust probability sample of stream segments is used to compare two small (20,000 hectare) subbasins of the Tillamook watershed, north coastal Oregon. The two subbasins are matched with respect to several variables [size coastal climates], but vary in terms of geology and consequently land use. A total of 67 wadeable + non-wadeable sizes were identified for sampling in the two subbasins (combined) over two field seasons from a sampling universe consisting of the River Reach File 3 (blue lines on 1:100,000 maps). Target variables include an extensive array of physical habitat endpoints, selected water chemistry endpoints, species composition, and relative abundance of both benthic macroinvertebrates and fish. Field protocols generally followed those of the U.S. EPA's Environmental Monitoring and Assessment Program (EMAP).Eleven fish species were encountered, a typically low number for coastal Oregon streams. Exploratory analysis using nonmetric multidimensional scaling revealed that 92.4% of the variation in the fish assemblages could be explained with two ordination axes. Environmental factors related to stream size and substate were the most correlated to these axes. Further, stream segments for the two subbasins tended to map in different areas of species space. Therefore, we also give unweighted probability distributions for several of the factors that heavily on these two axes by subbasins, as well as probability distributions for chemical endpoints. Results from the subset of sites sampled during the first year (21 wadeable sites) reveal: 1) differences between samples from the two subbasins relates to dream size and substrate composition that are consistent with known differences in geology and land use, 2) unexpectedly minor differences between samples from the two subbasins for stream temperature, canopy cover, and dissolved oxygen, 3) differences between samples from the two subbasins for total P, and total N, possibly related to land use, and 4) unexpected differences in samples from the two subbasins for conductivity, probably related to geological factors. Sample size for each subbasin is low and therefore our samples cannot be taken to necessarily characterize either subbasin. However, our findings are consistent with a comprehensive assessment that had been previously produced for one of the two subbasins.All field work was completed in 8 weeks 3-person field crew. We conclude that rapid assessment protocols, based on probability samples at this level of resolution, can be a cost-effective approach to watershed analysis. This approach should be seen as a complement to, rather than a replacement for, systematic surveys that produced finer scale, reach specific information on factors such as channel complexity and cover relevant to in-stream restoration planning.     

Distribution of heavy metals in Penaeus Semisulcatus from Persian Gulf and possible role of metallothionein in their redistribution during storage

The study was conducted between January and December 2002. The main objective of this study was evaluation of effects of refrigerated storage duration on redistribution of three trace elements (Cd, Cu and Zn) in tissues (exoskeleton, abdominal muscle and hepatopancreas) of a shrimp species (Penaeus semisulcatus). Moreover, the possible roles of metallothionein (a kind of metalloprotein) in redistribution of the elements in tissues of the selected species were assessed. The specimens were sampled from northwestern part of the Persian Gulf. The concentrations of metals in the tissues were measured using Inductively Coupled Plasma-Optical Emission Spectrophotometer (ICP-OES). Metallothionein levels were determined by Differential Pulse Polarography (DPP) method. pH of the muscle samples was also measured in different stages. Different statistical methods were used for interpretation of the results. There were no size-dependent differences in metal contents of the species. The results were compared with specimens from other areas of the world and existing guidelines and limits. Concentrations of the metals in the muscle (0.103, 3.418 and 8.977 µg g^–1 wet weight in the case of Cd, Cu and Zn, respectively) samples were below the most guidelines for human consumption. The results were in general agreement with those obtained by some other researchers. There were highly significant differences between sexes in Zn and Cu contents. Levels of Zn in females were significantly higher than males. The reverse case observed for Cu. The highest mean Cu and Zn concentrations (15.939 and 43.394 µg g^–1 wet weight, respectively) were found in hepatopancreas samples, but the highest level of Cd (0.790 µg g^–1 wet weight) was observed in exoskeleton. There were significant differences between the fresh and refrigerated samples from accumulation of Cd and Zn in tissues point of view, which can be attributed to the metal binding properties of metallothioneins as well as their degradation during the storage.     

Evaluation of analytical strategies for the determination of metal concentrations to assess landfill leachate contamination

Due to the complex nature of landfill leachates, metal and metalloid analyses prove to be tricky and suffer from a lack of standard protocols. A complete approach has been adopted to investigate the influence of the different steps during the sample processing of French landfill leachates. The validation of the entire protocol has been achieved using a laboratory reference material. This material, which is a real landfill leachate, is representative of real samples. Its evaluation has allowed a quality control for metal and metalloid analyses in landfill leachates. Precautions concerning storage temperature, aeration and filtration are proposed to perform accurate metal analyses in these complex matrices. The sample processing has been applied to the seasonal monitoring of a French landfill. The assessment of major leachate metallic contaminants such as As, Cr, Sb, Sn, has been performed by evaluating the relative enrichment of metals and metalloids in comparison with rain water and groundwater. In addition, hydrological data are useful and complementary information for pointing out the main factors affecting metal concentrations and thus their potential remobilisation pathways.