Approaches in measuring exposure to food contaminants

Measurement of levels of contaminants in food commodities and prepared meals, and market basket surveys are feasible in countries with existing systems of food control laboratories. Monitoring body tissues for contaminants or their metabolites reflects total exposure but care should be taken to select the most appropriate pharmacokinetic model.Strict quality control acquires particular value in obtaining (with existing instrumentation and facilities) results that meet specified acceptable parameters of analytical performance.Exposure measurement of dietary contaminants as a part of epidemiological studies becomes indispensable in the risk assessment process. Dietary intakes of DDT in USA and Bulgaria are within the range of virtually safe doses for liver tumors extrapolated from animal experiments by four low dose extrapolation models for risk levels of 10^-4 and 10^-6.     

Effect of organochlorine contaminants and individual biological traits on blubber retinoid concentrations in bottlenose dolphins (Tursiops truncatus)

Here we assessed retinoids as biomarkers of contaminant exposure by studying whether the sex, age, lipid content and organochlorine concentrations of bottlenose dolphins induced variation in retinoid status and its deposition in blubber. Blubber samples were collected from 47 individuals of known age and gender from Sarasota Bay in June 2000 and 2001. The sample included a representative cross-section of the resident dolphin community, with ages ranging from 2 to 50 years. Organochlorine levels showed the age- and sex-related variation commonly observed in other species, with concentrations increasing in youngsters of both sexes and in adult males, and decreasing in adult females after the onset of maturity. Blubber lipid content was low in the overall population and significantly decreased with age in adult males. Retinoid blubber concentrations were comparable to other odontocete species previously studied, and were strongly determined by lipid content. As a consequence of the latter, retinoid concentration was observed to decrease with age in adult males. This effect could not be statistically dissociated from the negative correlation observed between levels of organochlorines and retinoid blubber concentration. Consequently, we could not clarify whether high organochlorine loads in this population lowered retinoid concentrations or, conversely, whether depleted lipid reserves were indeed responsible for the high organochlorine concentrations and the low retinoid levels detected in blubber. With the current knowledge, both options should be considered and investigated, with initial focus on male dolphins.     

Inorganic and organic contaminants in Alaskan shorebird eggs

Many shorebird populations throughout North America are thought to be declining, with potential causes attributed to habitat loss and fragmentation, reduced prey availability, increased predation, human disturbance, and increased exposure to environmental pollutants. Shorebirds may be particularly vulnerable to contaminant exposure throughout their life cycle, as they forage primarily on invertebrates in wetlands, where many contaminants accumulate disproportionately in the sediments. Therefore, it is important to document and monitor shorebird populations thought to be at risk and assess the role that environmental contaminants may have on population declines. To investigate potential threats and provide baseline data on shorebird contaminant levels in Alaskan shorebirds, contaminant concentrations were evaluated in shorebird eggs from 16 species residing in seven geographic distinct regions of Alaska. Similar to previous studies, low levels of most inorganic and organic contaminants were found, although concentrations of several inorganic and organic contaminants were higher than those of previous studies. For example, elevated strontium levels were observed in several species, especially black oystercatcher (Haematopus bachmani) sampled in Prince William Sound, Alaska. Additionally, contaminant concentrations varied among species, with significantly higher concentrations of inorganic contaminants found in eggs of pectoral sandpiper (Calidris melanotos), semipalmated sandpiper (Calidris pusilla), black oystercatcher, and bar-tailed godwit (Limosa lapponica). Similarly, significantly higher concentrations of some organic contaminants were found in the eggs of American golden plover (Pluvialis dominica), black-bellied plover (Pluvialis squatarola), pacific golden plover (Pluvialis fulva), bar-tailed godwit, and semipalmated sandpiper. Despite these elevated levels, current concentrations of contaminants in shorebird eggs suggest that breeding environments are relatively free of most contaminants and that contaminant concentrations are below levels (except potentially strontium) that would likely affect the survival of individuals and consequently regulate the species at the population level.     

Characterisation of occupational exposure to air contaminants in a nitrate fertiliser production plant

The aim of this study was to characterise personal exposures to dust, acid vapours, and gases among workers in a Norwegian nitrate fertiliser production plant, as part of an ongoing epidemiological study. In total, 178 inhalable and 179 thoracic aerosol mass fraction samples were collected from randomly chosen workers (N = 141) from three compound fertiliser departments (A, B and C), a calcium nitrate fertiliser production department, nitric acid- and ammonia-production departments, and a shipping department. The overall median inhalable and thoracic aerosol mass concentrations were generally low (1.1 mg m(-3) (min-max: <0.93-45) and 0.21 mg m(-3) (min-max: <0.085-11), respectively). Workers at the compound fertiliser departments B and C had significantly higher inhalable aerosol mass air concentrations compared to the other departments (p < 0.05), except for compound fertiliser department A; however, the difference between the compound fertiliser department C and calcium nitrate department was slightly above the significant level. Workers at the compound fertiliser department A had significantly higher thoracic aerosol mass air concentrations compared to the other departments (p < 0.05), except for compound fertiliser departments B and C. The results indicate that the extrathoracic aerosol fraction of the aerosol compared to the thoracic fraction dominated in most departments. Measurement of the main constituents Ca, K, Mg, and P in the water-soluble and water-insoluble aerosol mass fractions showed that the air concentrations of these elements were low. There is, however, a shift towards more water-soluble species as the production goes from raw material with phosphate rock towards the final product of fertilisers. Overall, the arithmetic mean of water-soluble Ca in the thoracic mass fraction was 51% (min-max: 1-100). A total of 169 personal samples were analysed for HNO(3) vapour and HF. The highest median concentration of HNO(3) (0.63 mg m(-3)) was in the compound fertiliser departments B, and all measurements but four of the HF concentrations were below the LOD of 190 μg m(-3). Exposures to NH(3), CO and NO(2) were measured using direct-reading electrochemical sensors and the time weighted overall averages were all below the LODs of the respective sensors, NH(3) 2 ppm; CO 2 ppm; and NO(2) 0.2 ppm, but some short-term peaks were detected. Even though our results indicate that the workers may experience peak exposure episodes when performing job tasks such as cleaning or maintenance work, the overall air concentrations are well below what is considered to cause known health risks.     

Surfactant dissolution and mobilization of LNAPL contaminants in aquifers

Improper disposal, accidental spills and leaks of non-aqueousphase liquids (NAPL) such as gasoline, fuel oil and creosote result in long-term persistent sources of groundwater pollution.Column and 2-D tanks experiments were conducted to evaluate the use of surfactant-enhanced recovery of light non-aqueous phase liquids (LNAPL) in groundwater aquifers. These experiments focused on the use of surfactants to promote dissolution and mobilization in addition to evaluating the increase of aqueous phase permeability as residual NAPL is recovered. Further experiments are presented that show the innovative use of surfactants during primary pumping to recover free product canpotentially increase the amount of free product recovered, canpotentially reduce the amount of residual NAPL remaining afterprimary pumping and performs better than the use of surfactantsto mobilize trapped residual NAPL.     

Organic dust and gaseous contaminants at wood working shops

Airborne dust bioaerosols, ammonia and formaldehyde levels were determined inside two different (ventilated and unventilated) wood working shops. Airborne dust was found at mean values of 4.3 and 3.01 mg m(-3). These levels were higher than that recommended by Egyptian environmental law [1 mg m(-3) indoor maximum allowable concentration (MAC) for hard wood]. The highest frequency of aerodynamic size distribution of airborne wood dust was detected at a diametre of 4.9 microm which was recorded during a machining operation. Total viable bacteria were recorded at a mean value of 10(4) colony-forming units (cfu) m(-3), whereas Gram-negative bacteria were found at very low counts (10(1) cfu m(-3)). Fungi levels were recorded at mean values of 10(3) and 10(2) cfu m(-3) in ventilated and unventilated shops, respectively. Penicillium, Aspergillus, Cladosporium and yeast species were dominant isolates. Moreover, actinomycetes were found at a mean value of 10(3) cfu m(-3) at both workshops. Ammonia was detected in relatively low concentrations (mean values of 457 and 623 microg m(-3)), whereas formaldehyde was found in relatively moderate concentrations (mean values of 0.42 and 0.64 ppm).     

Survey design for lakes and reservoirs in the United States to assess contaminants in fish tissue

The National Lake Fish Tissue Study (NLFTS) was the first survey of fish contamination in lakes and reservoirs in the 48 conterminous states based on a probability survey design. This study included the largest set (268) of persistent, bioaccumulative, and toxic (PBT) chemicals ever studied in predator and bottom-dwelling fish species. The U.S. Environmental Protection Agency (USEPA) implemented the study in cooperation with states, tribal nations, and other federal agencies, with field collection occurring at 500 lakes and reservoirs over a four-year period (2000–2003). The sampled lakes and reservoirs were selected using a spatially balanced unequal probability survey design from 270,761 lake objects in USEPA’s River Reach File Version 3 (RF3). The survey design selected 900 lake objects, with a reserve sample of 900, equally distributed across six lake area categories. A total of 1,001 lake objects were evaluated to identify 500 lake objects that met the study’s definition of a lake and could be accessed for sampling. Based on the 1,001 evaluated lakes, it was estimated that a target population of 147,343 (±7% with 95% confidence) lakes and reservoirs met the NLFTS definition of a lake. Of the estimated 147,343 target lakes, 47% were estimated not to be sampleable either due to landowner access denial (35%) or due to physical barriers (12%). It was estimated that a sampled population of 78,664 (±12% with 95% confidence) lakes met the NLFTS lake definition, had either predator or bottom-dwelling fish present, and could be sampled.     

Approaches to soil remediation by complexometric extraction of metal contaminants with regeneration of reagents

Complexometric equilibrations were performed with six chelating reagents to mobilise Cu, Mn, Pb and Zn from a contaminated urban soil. The metal-laden aqueous extract was treated with sodium diethyldithiocarbamate (DEDTC) to precipitate the heavy metals from solution while liberating the chelating reagent. The aqueous supernatant fraction was then re-combined with the soil particulates to extract more pollutants. A sparing quantity of EDTA (ethylenediaminetetraacetic acid; 10 mmol) mobilised 32-54% of the 5 mmol of heavy metals from the soil with three cycles but only 0.1 and 1.0% of the iron and magnesium, respectively, was removed. Whereas DPTA (1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid) and citric acid also mobilised each of the heavy metals to some extent and continued to extract these metals during all three cycles, the DTPA (diethylenetriamine pentaacetic acid), although efficient initially, could not be recycled with these conditions. ADA [N-(2-acetamido)iminodiacetate] and SCMC [(S)-carboxymethyl-L-cysteine] were selective for copper and zinc but mobilised only Cu when recycled. An alternate means of regenerating the chelating reagent involved treatment of the aqueous extract with magnesium (Mg0) granules. Excess HEDC [bis(2-hydroxyethyl)dithiocarbamate] mobilised appreciable quantities (19-57%) of heavy metals from the soil and retained its complexing activity when recycled. An appreciable fraction of the mobilised Pb and Cu and a portion of the Zn were cemented to the surfaces of the excess magnesium whereas virtually all of the Fe and Mn was removed from solution as insoluble hydroxides.     

interactions amongst policies designed to resolve individual air issues

Six air issues are currently on science and policy agendas in Canadaand elsewhere. These are climate change, stratospheric ozone depletion(increased UV-B radiation), acidic deposition, SMOG (increasedground-level ozone), suspended particulate matter, and hazardous airpollutants. Atmospheric scientists and decision makers have largelyaddressed these issues individually resulting in single-issue policies. However, it is now recognized that these issues are inter-related, andthey may interact to cause negative as well as some beneficial effects,not only on the state of the atmosphere but also on societal andecological systems. This paper illustrates through several examples theatmospheric dysfunction caused by the linkages among the six airissues. It also points to potentially conflicting policies arising from thesingle-issue approach, and it emphasizes the need for better integrationof air issues. The linkages are summarized qualitatively in Table I.     

Stable isotope fractionation to investigate natural transformation mechanisms of organic contaminants: principles, prospects and limitations

Gas chromatography-isotope ratio mass spectrometry (GC-IRMS) has made it possible to analyze natural stable isotope ratios (e.g., (13)C/(12)C, (15)N/(14)N, (2)H/(1)H) of individual organic contaminants in environmental samples. They may be used as fingerprints to infer contamination sources, and may demonstrate, and even quantify, the occurrence of natural contaminant transformation by the enrichment of heavy isotopes that arises from degradation-induced isotope fractionation. This review highlights an additional powerful feature of stable isotope fractionation: the study of environmental transformation mechanisms. Isotope effects reflect the energy difference of isotopologues (i.e., molecules carrying a light versus a heavy isotope in a particular molecular position) when moving from reactant to transition state. Measuring isotope fractionation, therefore, essentially allows a glimpse at transition states! It is shown how such position-specific isotope effects are "diluted out" in the compound average measured by GC-IRMS, and how a careful evaluation in mechanistic scenarios and by dual isotope plots can recover the underlying mechanistic information. The mathematical framework for multistep isotope fractionation in environmental transformations is reviewed. Case studies demonstrate how isotope fractionation changes in the presence of mass transfer, enzymatic commitment to catalysis, multiple chemical reaction steps or limited bioavailability, and how this gives information about the individual process steps. Finally, it is discussed how isotope ratios of individual products evolve in sequential or parallel transformations, and what mechanistic insight they contain. A concluding session gives an outlook on current developments, future research directions and the potential for bridging the gap between laboratory and real world systems.     

Environmental contaminants in freshwater fish and their risk to piscivorous wildlife based on a national monitoring program

Organochlorine chemical residues and elemental concentrations were measured in piscivorous and benthivorous fish at 111 sites from large U.S. river basins. Potential contaminant sources such as urban and agricultural runoff, industrial discharges, mine drainage, and irrigation varied among the sampling sites. Our objectives were to provide summary statistics for chemical contaminants and to determine if contaminant concentrations in the fish were a risk to wildlife that forage at these sites. Concentrations of dieldrin, total DDT, total PCBs, toxaphene, TCDD-EQ, cadmium, chromium, mercury, lead, selenium, and zinc exceeded toxicity thresholds to protect fish and piscivorous wildlife in samples from at least one site; most exceedences were for total PCBs, mercury, and zinc. Chemical concentrations in fish from the Mississippi River Basin exceeded the greatest number of toxicity thresholds. Screening level wildlife risk analysis models were developed for bald eagle and mink using no adverse effect levels (NOAELs), which were derived from adult dietary exposure or tissue concentration studies and based primarily on reproductive endpoints. No effect hazard concentrations (NEHC) were calculated by comparing the NOAEL to the food ingestion rate (dietary-based NOAEL) or biomagnification factor (tissue-based NOAEL) of each receptor. Piscivorous wildlife may be at risk from a contaminant if the measured concentration in fish exceeds the NEHC. Concentrations of most organochlorine residues and elemental contaminants represented no to low risk to bald eagle and mink at most sites. The risk associated with pentachloroanisole, aldrin, Dacthal, methoxychlor, mirex, and toxaphene was unknown because NOAELs for these contaminants were not available for bald eagle or mink. Risk differed among modeled species and sites. Our screening level analysis indicates that the greatest risk to piscivorous wildlife was from total DDT, total PCBs, TCDD-EQ, mercury, and selenium. Bald eagles were at greater risk to total DDT and total PCBs than mink, whereas risks of TCDD-EQ, mercury, and selenium were greater to mink than bald eagle.     

Feasibility of relating interferon production by wild voles to types of chemical contamination of their environment

In the fall of 1980, a limited field sampling and laboratory analysis profect was undertaken to explore the feasibility of relating immunological responses of field mice (voles) living wild in an area of environmental concern to the level of chemical contamination of that area. The voles were collected in the vicinity of Love Canal by biological sampling teams already there to collect voles for other purposes.The project helped identify those areas of practical uncertainty that must be clarified before the rate of interferon production in voles can be considered as a possible indicator of chemical contamination. Two lines of research are proposed: developing optimumin vitro interferon bioassays systems for vole leukocytes; and characterizing the interferon production responses of voles following controlled exposures to selected carcinogens and other chemicals.     

Chlorobiphenyl contaminants at Pladda and Garroch Head in the Firth of Clyde in relation to sewage sludge input

Sewage sludge dumped at Garroch Head in the Firth of Clyde contains significant quantities of chlorinated hydrocarbons, such as polychlorinated biphenyls (CBs). These compounds are lipophilic and resistant to degradation. They accumulate in the biota either from the water column or through the food chain, particularly in tissue with a high lipid content. Bottom dwelling fish, such as plaice, in the vicinity of the dump site will accumulate CBs from their environment. Eighteen of the 209 CBs were measured in plaice livers from the Garroch Head dump site and from Pladda, a site reasonably remote from the dump site but also in the Clyde, over a 7 year period prior to the cessation of dumping in December 1998. Concentrations of the congeners in the liver of fish caught at the dump site were, in general, higher than those in the liver of fish caught at Pladda. Concentrations in the plaice livers for the sum of 18 CBs ranged from 1611 to 8471 micrograms kg-1 lipid for Garroch Head samples and from 336.9 to 2635 micrograms kg-1 lipid for samples from Pladda. The data were evaluated using principal component analysis (PCA). Pattern analysis was undertaken by normalising to the recalcitrant CB 153. Livers from the dump site were found to have a higher proportion of the lower chlorinated CBs. CB patterns were similar at the Garroch Head dump site from year to year, but multivariate techniques showed that there were differences in pattern when normalised to CB 153.     

Assessment of water systems for contaminants from domestic and industrial sewages

The State of Minas Gerais represents one of Brazil's most outstanding mining resources. The contamination of river waterfrom kaolin processing activities may be harmful to people inthe way of slow but chronic poisoning. On the other hand, the discharge of untreated or inadequately treated domestic sewage into aquatic environments can also cause deleterious effects to the health. However, no reliable figures are available for pollutant occurrences in river water. This draws attention to thevery precarious situation that exists with respect to pollutionby organic and inorganic toxic wastes, especially with respect to humans and fauna in all its expressions. Thus, with the purpose of establishing a preliminary report to trace out industrialisation outcomes, samples of river water, vegetation and fish were collected and analysed to detect pollutant inputs.The concentration of metals was determined in suspended particle,vegetation and fish, while those of nitrite, nitrate, phosphateand chloride were determined in river water samples. The concentration of dissolved oxygen (DO) was measured in river water at the time of collection. Chemical oxygen demand (COD) and biochemical oxygen demand (BOD) were also determined. Metalinputs in the samples analysed appeared to be related to effluentdischarges into the rivers. The suspended particles showed highconcentrations (in mg kg^-1) of zinc (62 600) and aluminium(559 000), while vegetation samples collected near rivers wereheavily contaminated with iron (7680). The fishes examined werecontaminated with chromium (1.5 mg kg^-1). In general, the concentrations of nitrite, nitrate, chloride, phosphate and BOD in river water were lower than the maximum values established bythe Brazilian Environmental Standards.     

Organophosphates in aircraft cabin and cockpit air--method development and measurements of contaminants

Methods for measurements and the potential for occupational exposure to organophosphates (OPs) originating from turbine and hydraulic oils among flying personnel in the aviation industry are described. Different sampling methods were applied, including active within-day methods for OPs and VOCs, newly developed passive long-term sample methods (deposition of OPs to wipe surface areas and to activated charcoal cloths), and measurements of OPs in high-efficiency particulate air (HEPA) recirculation filters (n = 6). In total, 95 and 72 within-day OP and VOC samples, respectively, have been collected during 47 flights in six different models of turbine jet engine, propeller and helicopter aircrafts (n = 40). In general, the OP air levels from the within-day samples were low. The most relevant OP in this regard originating from turbine and engine oils, tricresyl phosphate (TCP), was detected in only 4% of the samples (min-max 相似文献   

Normalization procedures for sediment contaminants in spatial and temporal trend monitoring

Rational pollution, or the effectiveness of natural attenuation assessments based upon estimating the degree of contamination, critically depends on the basis of a sound normalization to take into account heterogeneous sedimentary environments. By normalizing the measured contaminant concentration patterns for the sediment characteristics, the inherent variability can be reduced and so allow a more meaningful assessment of both the spatial distributions and the temporal trends. A brief overview and guidance in the methodology available for choosing an appropriate site-specific normalization approach is presented. This is followed by general recommendations with respect to the choice of normalizer and the necessary geochemical and statistical quality assurance methods, with support from the results of recent international intercomparison exercises within the QUASH (Quality Assurance of Sample Handling) programme, as well as discussions within the International Commission on the Exploration of the Sea (ICES) working groups. The most important of these recommendations is the use of a two-tiered normalization approach including wet sieving (<63 microm), followed by an additional geochemical co-factor normalization.     

Kriging for estimating spatial pattern of contaminants: Potential and problems

This paper discusses and illustrates the use of kriging techniques for estimating the spatial pattern of contaminants in environmental media, particularly soil. The assumptions underlying kriging are reviewed as are some advantages and disadvantages of the method. Lognormal kriging (kriging applied to logarithmic-transformed data) is illustrated using a set of radionuclide soil concentrations at a nuclear testing area on the Nevada Test Site. This example shows how lognormal kriging can be used to estimate average concentrations at points or for blocks of land, concentration contours over space, confidence bands about these contours, and radionuclide inventory in soil. The validity of kriging estimates depends on the accurate estimation and modeling of the spatial correlation structure of the phenomenon. Accuracy is especially important when lognormal kriging is used and estimates of means and their standard deviations are required in the original, untransformed scale. This paper illustrates the bias that can result when a changing correlation structure over space is ignored.Operated for the U.S. Department of Energy by Battelle Memorial InstituteWork supported by Nevada Applied Ecology Group, U.S. Department of Energy, Nevada Operations Office under Contract DE-AC06-76RLO 1830.     

Halogenated organic contaminants in marine fish and mussels from southern Greenland--pilot study on relations to trophic levels and local sources

Mussels and marine fish (shorthorn sculpin and Greenland cod) were sampled at three locations with varying human activity. Fish livers and mussels were analysed for polychlorinated biphenyls (PCBs), polybrominated diphenylethers (PBDEs) and chlorinated pesticides including chlordane and toxaphene. Levels of chlorinated contaminants in shorthorn sculpins from the background location, [capital Sigma]PCB (217-224 ng g(-1) lw), [capital Sigma]DDT (180 ng g(-1) lw) and hexachlorobenzene (32-44 ng g(-1) lw), were in the same range as previously observed in eastern Greenland but exceeded the levels previously observed in southern and western Greenland. Multivariate analysis showed that pollutant concentrations were mainly explained by trophic levels of the species (cod > sculpins > mussels). A pooled sample of shorthorn sculpins from the harbour of Qaqortoq had significantly higher PCB and PBDE concentrations with a different congener pattern compared to the background site, while other contaminants were comparable. This points towards local pollution sources, possibly accumulated emissions from burning of waste.     

Regional-scale models for relating land cover to basin surface-water quality using remotely sensed data in a GIS

Plant-based management systems implementing deep-rooted, perennial vegetation have been identified as important in mitigating the spread of secondary dryland salinity due to its capacity to influence water table depth. The Glenelg Hopkins catchment is a highly modified watershed in the southwest region of Victoria, where dryland salinity management has been identified as a priority. Empirical relationships between the proportion of native vegetation and in-stream salinity were examined in the Glenelg Hopkins catchment using a linear regression approach. Whilst investigations of these relationships are not unique, this is the first comprehensive attempt to establish a link between land use and in-stream salinity in the study area. The results indicate that higher percentage land cover with native vegetation was negatively correlated with elevated in-stream salinity. This inverse correlation was consistent across the 3 years examined (1980, 1995, and 2002). Recognising the potential for erroneously inferring causal relationships, the methodology outlined here was both a time and cost-effective tool to inform management strategies at a regional scale, particularly in areas where processes may be operating at scales not easily addressed with on-site studies.