Comments on 'Elevated antimony concentrations in commercial juices'

The recent J. Environ. Monit. communication 'Elevated antimony concentrations in commercial juices' contains several inaccuracies and misrepresentations about PET packaging as well as food safety and risk assessment. None of the data indicates that "elevated" or unsafe levels of antimony were found in any of the commercial juices or that the variations in antimony levels were attributable to either PET or the other packaging materials.     

The importance of small urbanized watersheds to pollutant loading in a large oligotrophic subalpine lake of the western USA

Urban land use has been implicated as a major contributor of nonpoint source pollution in aquatic systems. Through increased nonpoint delivery of pollutants, including constituents found in stormwater, Lake Tahoe is undergoing a marked decline in its transparency, primarily due to increasing production of algae from enhanced nutrient loading and delivery of fine particles to the lake from the watershed. In response to these findings, a regional restoration effort is underway to improve basin watersheds and the water quality in Lake Tahoe. In this study, stormwater autosamplers were used to collect flow-weighted composite samples that characterized event mean concentrations for event and nonevent conditions within a small, urbanized watershed in the Tahoe basin. An event-specified constant-concentration water quality model was then applied to the event mean concentration and continuous streamflow data to estimate pollutant loads for nitrate, nitrite, ammonia, orthophosphate, and suspended sediment. These data were compared with previously reported load estimates from 10 primary monitored streams in larger watersheds of the Tahoe basin. Results from a linear regression analysis demonstrate strong and significant relationships between watershed impervious area and pollutant loadings from Lake Tahoe watersheds. These small, urbanized watersheds and intervening zones, which only comprise 10 % of the total Lake Tahoe drainage area, include a significant portion of the total Lake Tahoe impervious area. The findings of this study suggest that small, urbanized watersheds and intervening zones are disproportionately important contributors of nonpoint source pollution, including nutrients and suspended particles.     

Trace metal and total suspended solids concentrations in freshwater: the importance of small-scale temporal variation

The temporal variation in the concentrations of particulate trace metals (Cu, Pb and Zn) and total suspended solids (TSS) was examined in three rivers that drain into the Port Jackson estuary, Australia, using a nested, hierarchical sampling design. Sampling was conducted between March and June 1999, under low flow conditions. The sampling design incorporated four temporal scales (hours, days, weeks and months). It was considered that hours, days, weeks and months were representative of such time scales and could be analyzed as random, nested sources of variation in an analysis of variance (ANOVA). Significant variation was found at temporal scales ranging from hours, within the same day, to months. The amount and scales of variation differed between particulate trace metals and TSS concentrations and between rivers. In many cases, differences between small-scale were as important as differences between months. The results suggest that higher anthropogenic influences cause higher variability at small temporal scale. Results indicate the need for nested sampling designs to be incorporated into studies of temporal variation in order to unconfound small-scale temporal variation. The conclusions of this study are likely to be applicable to other water quality variables and pollutants.     

Impact evaluation of agrotechnologies in watersheds

The special project RAISA (Advanced Researches for Innovation in Agricultural Systems) of the National Research Council of Italy concerns the development of new methodologies for the study and evaluation of the impact of agrotechnologies on the environment. In the project, several trans-disciplinary Units have worked together since 1990. The aim of the project is to define systems, using tools such as remote sensing and Geographical Information Systems, for decision making support in land planning and land use management, with particular attention to groudwater table pollution. The fundamental steps for evaluation of the impact of agrotechnologies on the Po river watershed, 75,000 km² in northern Italy, and Tevere (Tiber) river watershed, 17.169 km² in Central Italy are described here. The study concerns particular areas located in the western part of the Po River plain, where flooded rice is the main crop, and in the central plain of the Tevere basin where the risk of water pollution is considerable, due to small and medium sized swine breeding farms. The aspects considered were water pollution due to mineral nitrogen used to fertilize the rice crop and the nitrogen contained in the waste water from pig farms. For the Po river basin the methodology developed was based on the integration of satellite remote sensing images, and the available cartography, such as topographic and thematic maps, together with the hydrological and the toxicological data of the chemical fertilizers employed, summarized in maps of the groundwater table pollution hazard. A simpler evaluation was obtained in the Tevere river basin: the thematic layers were crossed in bi-directional matrices and the result merged with the map of the territorial distributionof the swine. In both cases the selected information was integrated and processed in Integrated sub-basin scale. The GISs led to the development of a user-friendly system for formalizing our knowledge of the degree of pollution hazard in simple and readable maps.Research supported by National Research Council of Italy, Special Project RAISA, sub-project N. 1 Paper N.     

Observations on the measurement of total antimony and antimony species in algae, plant and animal tissues

This paper describes our experiences with undertaking measurements of total antimony and antimony speciation in algae, plant and animal tissues. Digestion with nitric acid alone is suitable to release antimony from animal tissues. When organisms have high silica contents, e.g. some plants and algae, the addition of tetrafluorboric acid is required to dissolve silica as some antimony is retained by silica in extracts. Antimony in digested extracts is present as Sb5+ and hydride generation procedures can be used to determine total antimony concentrations, as total antimony in extracts will not be under estimated. Relatively non-aggressive solvents such as water, dilute nitric acid, sodium hydroxide and enzymes remove highly variable amounts of antimony (2-84%) from algae, plant and animal tissues. Addition of Sb3+ and Sb5+ to NIST CRM 1572 Citrus Leaves, pre- and post-extraction with water showed that Sb3+ is oxidised to Sb5+ while Sb5+ is redistributed amongst binding sites giving rise to artefacts. DOLT-2 and algae extracts indicated the presence of only inorganic antimony. A moss sample had inorganic antimony and a number of unknown antimony species in extracts. Future studies should explore the nature of the binding of antimony in tissues as solvents commonly used to extract metals and metalloids from algae, plant and animal tissues are not appropriate.     

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.     

Dissolved organic iodine in marine waters: role in the estuarine geochemistry of iodine

Non-volatile dissolved organic iodine (DOI) can be a major, or even the dominant, species of dissolved I in coastal, inshore and estuarine waters. It can be converted to IO3- in the presence of an oxidizing agent and to I- by reacting it with a reducing agent. Depending on the exact experimental conditions, the yields of these reactions may not be quantitative. In previous analytical schemes for the determination of IO3-, I- and DOI in marine waters, if oxidation or reduction steps are involved and the concentrations of one or more species are estimated by difference, the presence of DOI can lead to an overestimation of the concentrations of the inorganic species determined by difference and an underestimation of the concentration of DOI. In two cruises covering the James River to the southern Chesapeake Bay and from the southern Chesapeake Bay to the Atlantic, above a salinity (S) of 2, the contribution of DOI to total I increased with decreasing salinity and reached a maximum of 80%. DOI, I- and IO3- were successively the dominant form of dissolved I at 0.1 < S < 15 in the James River estuary, 15 < S < 30 in the Southern Chesapeake Bay and S > 30 in the Atlantic Ocean at the Bay mouth, respectively. Total I behaved conservatively (i.e., no evidence of consumption or production) during estuarine mixing during both cruises. In the southern Chesapeake Bay, total inorganic I was also approximately conservative. The primary process affecting the speciation of dissolved I was the conversion of IO3- to I-. In the James River estuary, there were indications of the conversion of both IO3- and I- to DOI. The concentrations of total I, IO3-, I- and DOI in James River water were 0.121, undetectable, 0.068 and 0.053 microM, respectively. These concentrations of total I and I- are significantly higher while that of IO3- is noticeably lower than those used presently for estimating global riverine input of these I species to the oceans. The riverine flux of DOI to the oceans is presently unknown.     

Analysis of diazinon monitoring data from the Sacramento and Feather River watersheds: 1991-2001

The objectives of this study were to: (1) analyzehistorical diazinon water column monitoring data frominconsistent monitoring programs in mainstem and tributary sitesin the Sacramento and Feather River watersheds from 1991 to 2001to assess possible spatial and temporal trends and (2) determinethe probability of measured diazinon concentrations by site orsimilar pooled sites exceeding various proposed effectsbenchmarks such as Water Quality Criteria and 10th centilesderived from species sensitivity distributions proposed as targetconcentrations for Total Maximum Daily Loads (TMDLs). An analysisof diazinon monitoring data from both fixed and rain eventsampling from the Sacramento/Feather River watersheds from 1991to 2001 showed that 90th centiles for 27 different mainstemand tributary sites ranged from 12 to 14,897 ng L^-1. The 90th centiles were generally higher at tributary sites (as compared to mainstem sites) during rain event sampling prior to 1995. A comparison of rain event samples for similar sites sampled in 1994 and 2000 showed that 90th centiles were lower in seven of eight sites in 2000. A comparison of pooled mainstemsites between 1994 and 2000 for rain event data showed a lower90th centile value for 2000; 90th centiles were alsolower in 2000 at all pooled tributary sites and all sites whendata from a highly influential site was removed. For varioussite designations (all sites, pooled mainstem sites etc.) theprobability of exceeding the acute and chronic diazinon targetsdeveloped by California Department of Fish and Game decreasedfrom 1994 to 2000. These data clearly show progress in the 6 yrperiod in reducing environmental concentrations of diazinon.Probability of exceeding the 10th centile targets based onspecies sensitivity distributions for arthropods (the mostsensitive taxa to diazinon exposure) was similar and fairly lowbetween years; the highest percent probability of exceedance forany site designation was 20%.Results from a two-way ANOVA using individual measurementsfrom all sites sampled showed a significant decrease during rainevents between 1994 and 2000, although the decrease was notequivalent for all sites. Sources of uncertainty identified inthe analysis of rain event data from 1994 and 2000 wereinconsistent frequency of sampling during rain events for eachyear, unknown definition of rain events between the two years andnon-defined measurement point within the hydrograph of rainevents sampled in each year. Analysis of diazinon trends fromfixed sampling was limited due to lack of yearly data by site;therefore, only parametric analysis could be conducted. Based onparametric analysis of diazinon monitoring data from fixedsampling sites, the percent detected concentrations were greaterthan 20% for 12 tributary sites and 5 mainstem sites fromsamples collected during January-March. On the average over allsites and months, diazinon concentrations have decreased at fixedsampling sites in the Sacramento/Feather River watershed from1991 to 2001.     

Methodologies for determination of antimony in terrestrial environmental samples

Methodologies for the environmental analysis of total antimony and aqueous chemical speciation are critically reviewed, including preparation techniques for aqueous and solid matrices and the determination of solid state partitioning and recommendations are given for future research directions. Concentrations of total antimony commonly present in aqueous and solid environmental samples are readily determined using present day analytical techniques. This has resulted primarily from technological advances in microwave digestion for solid matrices and the development of plasma based analyte detection systems. ICP-AES and ICP-MS techniques are both utilised for the environmental analysis of total antimony concentrations. However, ICP-MS is increasingly favoured as a result of reduced spectral interferences and the potential for analyte detection in the pg mL(-1) range. Determination of aqueous antimony speciation presents a number of complex analytical challenges and highly selective separation and identification techniques are required prior to detection. The majority of published techniques including common applications of hydride generation are insufficiently selective for the determination of intrinsic chemical speciation and often only oxidation state data are obtained. The recent in-line applications of HPLC-ICP-MS offer the potential for highly selective separations of aqueous antimony species and determination of detailed chemical speciation data. However, considerable development work is required to optimise chromatographic separations and identify uncharacterised species resident in environmental systems. Analytical techniques to aid the determination of antimony's associations with solid environmental matrices include the application of chemical extraction procedures and leaching experiments. To date, this area of analytical research has received little attention and further studies are required to elucidate this aspect of antimony's environmental chemistry.     

Predicting the biological condition of streams: use of geospatial indicators of natural and anthropogenic characteristics of watersheds

We developed and evaluated empirical models to predict biological condition of wadeable streams in a large portion of the eastern USA, with the ultimate goal of prediction for unsampled basins. Previous work had classified (i.e., altered vs. unaltered) the biological condition of 920 streams based on a biological assessment of macroinvertebrate assemblages. Predictor variables were limited to widely available geospatial data, which included land cover, topography, climate, soils, societal infrastructure, and potential hydrologic modification. We compared the accuracy of predictions of biological condition class based on models with continuous and binary responses. We also evaluated the relative importance of specific groups and individual predictor variables, as well as the relationships between the most important predictors and biological condition. Prediction accuracy and the relative importance of predictor variables were different for two subregions for which models were created. Predictive accuracy in the highlands region improved by including predictors that represented both natural and human activities. Riparian land cover and road-stream intersections were the most important predictors. In contrast, predictive accuracy in the lowlands region was best for models limited to predictors representing natural factors, including basin topography and soil properties. Partial dependence plots revealed complex and nonlinear relationships between specific predictors and the probability of biological alteration. We demonstrate a potential application of the model by predicting biological condition in 552 unsampled basins across an ecoregion in southeastern Wisconsin (USA). Estimates of the likelihood of biological condition of unsampled streams could be a valuable tool for screening large numbers of basins to focus targeted monitoring of potentially unaltered or altered stream segments.     

An assessment of benthic condition in several small watersheds of the Chesapeake Bay, USA

We examined benthic condition in three small watersheds in the Chesapeake Bay. Characterization of benthic condition was based on the combined measurements of benthic fauna, sediment toxicity, and sediment contaminant loads. Significant differences between watersheds were detected for sediment contaminant concentrations and water quality. The intensity of benthic impairment was greatest in the river surrounded by the most developed watershed. Spatial patterns of benthic condition were detected within all three watersheds. In contrast to current, intense focus on nutrient pollution in the Chesapeake Bay, qualitative comparison of our findings to land-use patterns supports findings of other studies that suggest benthic condition in tributaries of the Chesapeake Bay may more closely relate to urbanization than agricultural land uses.     

Reproductive health indicators of fishes from Pennsylvania watersheds: association with chemicals of emerging concern

Fishes were collected at 16 sites within the three major river drainages (Delaware, Susquehanna, and Ohio) of Pennsylvania. Three species were evaluated for biomarkers of estrogenic/antiandrogenic exposure, including plasma vitellogenin and testicular oocytes in male fishes. Smallmouth bass Micropterus dolomieu, white sucker Catostomus commersonii, and redhorse sucker Moxostoma species were collected in the summer, a period of low flow and low reproductive activity. Smallmouth bass were the only species in which testicular oocytes were observed; however, measurable concentrations of plasma vitellogenin were found in male bass and white sucker. The percentage of male bass with testicular oocytes ranged from 10 to 100 %, with the highest prevalence and severity in bass collected in the Susquehanna drainage. The percentage of males with plasma vitellogenin ranged from 0 to 100 % in both bass and sucker. Biological findings were compared with chemical analyses of discrete water samples collected at the time of fish collections. Estrone concentrations correlated with testicular oocytes prevalence and severity and with the percentage of male bass with vitellogenin. No correlations were noted with the percentage of male sucker with vitellogenin and water chemical concentrations. The prevalence and severity of testicular oocytes in bass also correlated with the percent of agricultural land use in the watershed above a site. Two sites within the Susquehanna drainage and one in the Delaware were immediately downstream of wastewater treatment plants to compare results with upstream fish. The percentage of male bass with testicular oocytes was not consistently higher downstream; however, severity did tend to increase downstream.     

Phytoplankton distribution during two contrasted summers in a Mediterranean harbour: combining automated submersible flow cytometry with conventional techniques

Present study was conducted in rapidly growing city Islamabad, and surface soils were collected from three major land cover types viz., built-up, drain side, and green areas. A total of seven physicochemical parameters and 11 metals were determined in surface soils. Factor analysis based on principal component analysis explained total variance of 68.0%, 64.5%, and 60.2% of three land cover types and showed high loadings for major elements (Mg and K) in built-up and green area and Fe in drain side. Top soil pollution index was carried out by using geo-accumulation index and metal pollution index (MPI₆). Concentration of major elements (Ca, Mg, Na, K) in surface soils is derived by parent material, whereas concentration of Fe, Ni, Pb, and Zn were mainly related with anthropogenic sources. Geostatistical methods such as kirging identified hotspot areas of metal contamination by Pb, Ni, and Zn in built-up areas influenced mainly by vehicular emissions and waste disposal. The results stresses that land clearing should be avoided to reduce contamination and management of urban soils.     

Behaviors of dissolved antimony in the Yangtze River Estuary and its adjacent waters

Antimony is a naturally occurring and cumulatively toxic element. With increasing concern as an inorganic contaminant, research on its environmental behavior is becoming a necessity. However, very little is known about this element. To further understand its biogeochemical behaviors and roles in the ecosystem, the main species of dissolved inorganic antimony (Sb(iii) and Sb(v)) in Yangtze River Estuary and its adjacent waters were determined by hydride generation and atomic fluorescence (HG-AFS) in our study. Results show that in surface water, the concentration for Sb(iii) and Sb(v) were in the range 0.029 μg L(-1)～ 0.736 μg L(-1) and 0.121 μg L(-1)～ 2.567 μg L(-1), with averages of 0.152 μg L(-1) and 0.592 μg L(-1), respectively. While concentrations of Sb(iii) and Sb(v) in the bottom layer were much lower, ranging from 0.023 μg L(-1) to 0.116 μg L(-1) (average of 0.050 μg L(-1)) and from 0.047 μg L(-1) to 0.441 μg L(-1) (average of 0.194 μg L(-1)), respectively. Data analysis further demonstrates that the major processes controlling antimony geochemistry in the area are riverine input, atmospheric deposition, incursion of Taiwan Warm Current, and release from particulate phase. The surface-enrichment and bottom-depletion depth profile reveals it does appear as a mildly scavenged element but is less like arsenic than previously believed. Sb(v) was the predominant speciation in aquatic environment of our research, and Sb(iii) was a minor constituent of the total antimony. Regarding the adsorption-desorption process onto SPM, Sb(iii) has a higher affinity to particulate phase than Sb(v). Furthermore, the significant correlation between antimony and nutrients indicates it is an element with great biological potential, which is also an important behavior for antimony.     

Land cover change of watersheds in Southern Guam from 1973 to 2001

Land cover change can be caused by human-induced activities and natural forces. Land cover change in watershed level has been a main concern for a long time in the world since watersheds play an important role in our life and environment. This paper is focused on how to apply Landsat Multi-Spectral Scanner (MSS) satellite image of 1973 and Landsat Thematic Mapper (TM) satellite image of 2001 to determine the land cover changes of coastal watersheds from 1973 to 2001. GIS and remote sensing are integrated to derive land cover information from Landsat satellite images of 1973 and 2001. The land cover classification is based on supervised classification method in remote sensing software ERDAS IMAGINE. Historical GIS data is used to replace the areas covered by clouds or shadows in the image of 1973 to improve classification accuracy. Then, temporal land cover is utilized to determine land cover change of coastal watersheds in southern Guam. The overall classification accuracies for Landsat MSS image of 1973 and Landsat TM image of 2001 are 82.74% and 90.42%, respectively. The overall classification of Landsat MSS image is particularly satisfactory considering its coarse spatial resolution and relatively bad data quality because of lots of clouds and shadows in the image. Watershed land cover change in southern Guam is affected greatly by anthropogenic activities. However, natural forces also affect land cover in space and time. Land cover information and change in watersheds can be applied for watershed management and planning, and environmental modeling and assessment. Based on spatio-temporal land cover information, the interaction behavior between human and environment may be evaluated. The findings in this research will be useful to similar research in other tropical islands.