Pesticides of Potential Ecological Concern in Sediment from South Florida Canals: An Ecological Risk Prioritization for Aquatic Arthropods

A two-tier ecological risk assessment was conducted for pesticides monitored in sediment at 36 sampling sites in south Florida freshwater canals from 1990–2002. For tier 1, we identified the chemicals of potential ecological concern (COPECs) as DDT, DDD, DDE, chlordane and endosulfan based on their exceedence of sediment quality standards at 20 sites. For 12 sites with data on the fraction of organic carbon in sediments, whole sediment concentrations of COPECs were converted to pore water concentrations based on equilibrium partitioning. In tier 2, a probabilistic risk assessment compared distributions of pore water exposure concentrations of COPECs with effects distributions of freshwater arthropod response data from laboratory toxicity tests. Arthropod effects distributions included benthic and non-benthic arthropod species for chlordane (n = 9), DDD (n = 12), DDE (n = 5), DDT (n = 48), and endosulfan (n = 26). The overlap of predicted pore water concentrations and arthropod effects distributions was used as a measure of risk. DDE was the most frequently detected COPEC in sediment at the 12 sites. Chlordane was present at only one site. The mean 90th centile concentration for pore water exposure was highest for endosulfan and lowest for DDT. The estimated acute 10th centile concentration for effects was highest for chlordane and lowest for DDD. The probability of pore water exposures of COPECs exceeding the estimated 10th centile concentrations for species sensitivity distributions of arthropod acute toxicity data was between 0 and 1%. The estimated NOEC 10th centile concentration from arthropod chronic toxicity distributions was exceeded by the estimated 90th centile concentration for pore water distributions at three sites. Endosulfan had the highest potential chronic risk at S-178 in the C-111 canal system, based on the probability of pore water exposure concentrations exceeding the arthropod estimated chronic NOEC 10th centile at 41%. The COPEC with the next highest probability of exceeding the chronic NOEC 10th centile was DDD at 17.7% and 19.8% in the Everglades Agricultural Area (at S-2 and S-6). DDT had minimal potential chronic risk. Uncertainties in exposure and effects analysis and risk characterization are discussed.     

Aquatic Risk Assessment of Metals in Sediment from South Florida Canals

A major watershed restoration effort is underway in south Florida, yet there are significant gaps in scientific information on exposure and risks of contaminants to its natural resources. We conducted a two-tier aquatic screening-level ecological risk assessment for metals that were monitored in sediment at 32 sampling sites in south Florida freshwater canals from 1990–2002. For tier 1, the chemicals (or metals) of potential ecological concern (COPECs) were identified as arsenic, cadmium, chromium, copper, lead, nickel and zinc based on their exceedences of Florida sediment quality guidelines at 10 sites. For tier 2, we used a probabilistic risk assessment method to compare distributions of predicted pore water exposure concentrations of seven metal COPECs with distributions of species response data from laboratory toxicity tests to quantify the likelihood of risk. The overlap of pore water concentrations (90th centile for exposure) for metal COPECs and the effects distributions for arthropods (10th centile of LC50s) and all species (10th centile of chronic NOECs) were used as a measure of potential acute and chronic risks, respectively. Arsenic (25%) in the Holey Land tracts, in Broward County north of Everglades National Park (ENP), and chromium (25%) in the C-111 freshwater system, at the east boundary of ENP, were the most frequently detected COPECs in sediment. Antimony (6%), zinc (6%) and lead (5%) were the least frequently detected COPECs in sediment. The 90th centile concentrations for bulk sediment were highest for zinc (at S-178) and lead (at S-176) in the C-111system. The 90th centile concentration for pore water exposure was highest for arsenic in the Holey Land tracts and lowest for cadmium and chromium. The estimated acute 10th centile concentration for effects was lowest for copper and arthropods. The probabilities of pore water exposures of copper exceeding the estimated acute 10th centile concentration from the species sensitivity distributions (SSD) of acute toxicity data (for arthropods) were 57 and 100% for copper at S-177 and S-178 in the C-111 system, respectively. The probability of pore water exposures of copper exceeding the estimated NOEC 10th centile concentration from the SSD of chronic toxicity data (for all species) was 93 and 100% for copper at S-177 and S-178, respectively. Uncertainties in exposure and effects analysis and risk characterization are identified and discussed. The study presents a straightforward approach to estimate exposure and potential risks of metals detected in sediment from south Florida canals.     

Are all distributions of risk with the same 95thpercentile equally acceptable?

When evaluating a probabilistic health risk assessment, say at a hazardous waste site, risk managers need a risk management policy that distinguishes an acceptable distribution of risks to individuals in a population from an unacceptable one. If a risk manager decides that the distribution of risk for the status quo is unacceptable, then a risk assessor needs a way to compute cleanup targets, i.e., the risk assessor needs a policy statement against which to estimate distributions of exposure point concentrations which, if engineered at a site, will achieve an acceptable distribution of risk. Some regulatory agencies base acceptability on whether the 95^th percentile of the risk distribution falls at or below a given value, without considering the behavior of the rest of the distribution. As regulatory agencies adopt risk management policies for use with probabilistic risk assessments, we recommend that they base their new policies on two simultaneously binding constraints‐one on an upper percentile and one on the arithmetic mean of the distribution of risk‐in addition to other non‐risk criteria.     

Risk assessment of polycyclic aromatic hydrocarbons (PAHs) in sediments from a mixed-use reservoir

Although reservoirs in China are of great significance, very few studies on risk assessment have been reported for reservoirs. This study investigated distribution characteristics, cancer and ecological risks, and source diagnosis of 16 priority polycyclic aromatic hydrocarbons (PAHs) in sediments from Shitou Koumen Reservoir in Jilin Province, China. A total of 12 sediment samples were collected from the reservoir in August (wet season) 2014. Total PAH concentrations in sediment samples ranged from 1294.51 ng/g to 2755.35 ng/g with a mean concentration of 1757.54 ng/g. For individual PAHs, average concentration of Nap was the highest, 800.56 ng/g, while Acy, Fla, BkF, and DahA were undetected in sediment samples. Light PAHs (2–3 rings) accounting for 74.21% was a dominant PAH compositional pattern. Pearson correlation analysis was carried out; results showed that total PAHs was strongly correlated with the highly enriched sedimentary PAHs, and pH was a major factor in controlling PAH distribution. Lifetime cancer risk was employed to assess cancer risk; results indicated that the fish-culturing area was exposed to cancer risk. The molecular diagnostic ratios of isomeric PAHs were applied to identify possible PAH sources; primary PAH sources were identified as oil-related activities, burning agricultural wastes, vehicular emissions, and industrial discharges.     

Impact of Random Variables Probability Distribution on Public Health Risk Assessment from Contaminated Soil

Probabilistic methods are now being applied increasingly to public health risk assessment instead of the deterministic, conservative, point estimates. An essential part of the probabilistic methods is the selection of probability distribution functions to represent the uncertainty of the random variables considered. We study the effect of selection of different probability distribution functions on the probabilistic outcome using the first-order reliability method (FORM). An example of cancer risk resulting from dermal contact with benzo(a)pyrene (BaP)-contaminated soil is given. Cancer potency factor, soil concentration, and fraction of skin area exposed were assigned normal, lognormal, and uniform probability distribution functions, and the effect of probability of exceeding a target risk level (termed the probability of failure) and sensitivity measures were studied. We investigated the question: what happens when one assumes different distribution shapes with the same mean and standard deviation? The results indicate that the selection of a probability distribution function for the random variables had a moderate impact on the probability of failure when the target risk is at the 50th percentile level, while the impact was much larger for a 95th target risk percentile. We conclude that the probability distribution will have a large impact because in most cases the regulatory threshold risk is at the tail end of the risk distribution. The impact of the distributions on probabilistic sensitivity, however, showed a reversed trend, where the impact was slightly more appreciable for the 50th percentile than for the 95th percentile. The selection of distribution shape did not, however, alter the order of probabilistic sensitivity of the basic random variables.     

Predictive Value of Species Sensitivity Distributions for Effects of Herbicides in Freshwater Ecosystems

In this article we present a review of the laboratory and field toxicity of herbicides to aquatic ecosystems. Single-species acute toxicity data and (micro)mesocosm data were collated for nine herbicides. These data were used to investigate the importance of test species selection in constructing species sensitivity distributions (SSDs), and in estimating hazardous concentrations (i.e., HC5) protective for freshwater aquatic ecosystems. A lognormal model was fitted to toxicity data (acute EC50s and chronic NOECs) and the resulting distribution used to estimate lower (95% confidence), median (50% confidence), and upper (5% confidence), HC5 values. The taxonomic composition of the species assemblage used to construct the SSD does have a significant influence on the assessment of hazard and only sensitive primary producers should be included for the risk assessment of herbicides. No systematic difference in sensitivity between standard and non-standard test species was observed. Hazardous concentrations estimated using laboratory-derived acute and chronic toxicity data for sensitive freshwater primary producers were compared to the response of herbicide-stressed freshwater ecosystems using a similar exposure regime. The lower limit of the acute HC5 and the median value of the chronic HC5 were protective of adverse effects in aquatic micro/mesocosms even under a long-term exposure regime. The median HC5 estimate based on acute data was protective of adverse ecological effects in freshwater ecosystems when a pulsed or short-term exposure regime was used in the microcosm and mesocosm experiments. There was also concordance between the predictions from the effect model PERPEST and the concentrations at which clear effects started to emerge in laboratory and field studies. However, compared to the SSD concept, the PERPEST model is able to provide more information on ecological risks when a common toxicological mode of action is evaluated as it considers both recovery and indirect effects.     

The Concentration Term and Derivation of Cleanup Goals Using Probabilistic Risk Assessment

This communication examines the role of back-calculation in developing a cleanup goal from a probabilistic risk assessment. Although back-calculation is not always appropriate with a Monte Carlo analysis, if the target risk level is specified as a single value (e.g., 95% of the population must have a cancer risk below 10?5), then back-calculation can be used to solve for a cleanup goal that represents an average concentration for an exposure area consistent with the stated target risk. This rule applies in developing screening levels and in probabilistic risk assessments that examine the influence of uncertainty in the average concentration. Back-calculation is not used to develop cleanup goals when risks arising from variable concentrations are assessed, for example, when exposure areas are very small such as for some ecological receptors, or when exposure frequency is very low such as for tourist fishermen. In this case, the cleanup goal is derived from an iterative risk calculation considering various possible truncation values of the concentration distribution. A cleanup goal derived in this manner does not correspond to a required average, but rather represents the maximum concentration that should be left in the field. Finally, although single value target risk specifications are common today, there may be advantages to setting target risks for multiple percentiles of the population, complicating the effort to calculate a cleanup goal.     

Frequency distribution of coliforms in water distribution systems.

Nine small water distribution systems were sampled intensively to determine the patterns of dispersion of coliforms. The frequency distributions of confirmed coliform counts were compatible with either the negative-binomial or the lognormal distribution. They were not compatible with either the Poisson or Poisson-plus-added zeroes distribution. The implications of the use of the lognormal distributional model were further evaluated because of its previous use in water quality studies. The geometric means from 14 data sets ranged from 10(-6) to 0.2 coliforms per 100 ml, and the geometric standard deviations were between 10 and 100, with one exception. If the lognormal model is representative of the coliform distribution; the arithmetic mean sample count is a poor estimator of the true mean coliform density, and the probability of water in a distribution system containing small patches with large coliform densities without detection by routine monitoring is finite. These conclusions have direct bearing on the interpretation of microbiological quality standards for drinking water.     

Probabilistic Risk Assessment and Risk Mapping of Sediment Metals in Sydney Harbour Embayments

Sediment metal concentrations in embayments of Sydney Harbour, acquired from the literature and from samples collected for this study, were used to generate contaminant probability density distributions using AQUARISK. The sediment metal concentrations often exceeded Australia's interim sediment quality guidelines. Similarly, estuarine spiked sediment toxicity test literature provided adverse biotic effects concentration data to generate species sensitivity distributions using AQUARISK. Although the harbor is subject to other inorganic and organic contamination, we have used sediment metals to demonstrate an approach for ecological risk mapping and environmental management prioritization. Sufficient spiked sediment toxicity test data were found for only three metals—Cd, Cu, and Zn—and some tests were likely to overestimate toxicity. The estimates of the hazardous concentration to 5% of species (the 50th percentile of the 95% species protection level) were 5, 12, and 40 mg/kg DW of total sediment metal for Cd, Cu, and Zn, respectively. These values were generally low when compared with the interim sediment quality guidelines due to the overestimation of toxic effects in the literature data. The parameters for the species sensitivity distributions have been combined with the measured sediment metal concentrations in Homebush Bay to generate risk maps of the estimated species impact for each metal as well as for all three metals collectively assuming proportional additivity. This has demonstrated the utility of comparing contaminants on a consistent scale—ecological risk.     

A Novel Approach to Determining a Population-Level Threshold in Ecological Risk Assessment: A Case Study of Zinc

A novel approach to population-level assessment was applied in order to demonstrate its utility in estimating and managing the risk of zinc in a water environment. Much attention has been paid to population-level risk assessment, but there have been no attempts to determine a “safe” population-level concentration as an environmental criterion. Based on the published results of toxicity tests for various species, we first theoretically derived a threshold concentration at which a population size is unchanged due to the adverse effects of zinc exposure. To derive a zinc concentration that will protect populations in natural environments, we adopted the concept of species sensitivity distribution. Assuming the threshold concentrations of a set of species are log-normally distributed, we calculated the 95% protection level of zinc (PHC₅ :population-level hazardous concentration of 5% of species), which is 107 μg/L. Meanwhile, the 95% protection criterion (HC₅) based on conventional individual-level chronic toxicity, was calculated to be 14.6 μg/L. The environmentally “safe” concentration for a population-level endpoint is about 7 times greater than that for an individual-level endpoint. The proposed method provides guidance for a pragmatic approach to population-level ecological risk assessment and the management of chemicals.     

Human health risk assessment and source diagnosis of polycyclic aromatic hydrocarbons (PAHs) in the corn and agricultural soils along main roadside in Changchun,China

This work was to investigate distribution characteristics, human health risk assessment, and possible sources of 16 priority polycyclic aromatic hydrocarbons (PAHs) in corn and surface soils of farmlands along main roadside in Changchun City, Jilin Province, China. Total concentrations of 16 PAHs ranged from 1572.4 to 4390.2 µg/kg with a mean value of 2954.9 µg/kg in soils and from 219.9 to 627 µg/kg with a mean value of 362µg/kg in corn. Light-molecular-weight PAHs (2–3 rings) concentration was dominant in soils, accounting for 51%, whereas high-molecular-weight PAHs (5–6 rings) concentration was highest in corn, accounting for 48%. The results of plant concentration factor indicated that high-molecular-weight PAHs have greater mobility. To evaluate potential risk to human health, hazard index (HI) and risk index (RI) were employed. The values of HI for corn and soils were both smaller than 1, indicating that exposure of PAHs posed no or little potential risk to local residents. The fact that values of RI for corn and soils were smaller than 1 × 10^–4 suggested that exposure of PAHs posed no or little cancer risk to local residents. The possible sources of PAHs in corn and soils were both identified as mixture patterns of pyrogenic and petrogenic sources.     

Urinary Fluoride Reference Values Determined by a Fluoride Ion Selective Electrode

As fluoride has a very short half-life in the body and the major route for fluoride excretion is via the kidney, human exposure is best measured in urine, where the concentration is expected to be highest. The urinary fluoride concentrations of 167 healthy Japanese adults were determined by means of a fluoride ion selective electrode. When the results were corrected for a specific gravity ρ = 1.024 g cm⁻³, the histogram of urinary fluoride concentrations highly skewed toward low values with sharp peakedness (skewness = 1.56, kurtosis = 3.08). The normality of the log-transformed histogram (skewness = 0.12, kurtosis = 0.07) and the straight line on log-probability paper clearly showed a key feature of lognormal distribution of urinary fluoride. A geometric mean (GM) of 613.8 μg/l and 95% confidential interval (CI) of 241.0–1633.1 μg/l were established as reference values for urinary fluoride. The results presented in this study will be useful as guidelines for the biological monitoring of fluoride in normal subjects and individuals at risk of occupational or environmental fluoride exposure.     

Contamination and environmental risk assessment of heavy metals in marine sediments from Tahaddart estuary (NW of Morocco)

Abstract

The distribution, contamination status, and ecological risks of heavy metals in Tahaddart estuary were investigated. 24 surface sediment samples and two cores were collected and analyzed for major (Al and Fe), heavy metals (As, Cd, Cr, Cu, Ni, Pb, and Zn), and grain size composition. The heavy metals assessment was carried out using different environmental indices. The results indicated that the spatial distribution patterns of Al, Fe, and Zn were mainly determined by the distribution of the finer grained fraction (<63?μm) in the sediment. In contrast, As, Cd, Cr, Cu, Ni, and Pb concentrations were controlled by anthropogenic activities (vehicular traffic from Highway Bridge and thermal power plant). The distribution of heavy metals in sediment cores showed an upward enrichment in heavy metals with high concentration found in the uppermost may related to the increasing in human activities. The pollution indexes confirmed that the Tahaddart estuary sediment was considerably to high contaminated by heavy metals near to different anthropogenic inputs. Similarly, the potential ecological risk index and the biological risk index present 21% probability of toxicity posing potential risk to the aquatic organisms. These results provide basic information that can be used to protect and improve the quality of this ecosystem.     

A parametric distribution for the fraction of outdoor soil in indoor dust

For a chemical that does not have a source inside a house, the ratio of its dust concentration indoors to its soil concentration outdoors is equal to the fraction of house dust that is composed of soil. To estimate the fraction of soil in house dust, we compiled ratios of the concentrations of a chemical in dust and soil from the scientific literature. We find that a lognormal distribution fits the data extremely well. This distribution is suitable for use in public health risk assessments for single‐family homes in temperate climates.     

Comparison of the Long-Term Risks of Removal and In Situ Management of Contaminated Sediments in the Fox River

The long-term potential risks of environmental dredging vs. in situ contaminated sediment management practices are discussed and compared for the Lower Fox River, Wisconsin. The risks are identified as being largely associated with the residual sediment contamination associated with either approach. The integral of the surface area-weighted average contaminant concentration in surface sediment is proposed as a metric to compare these risks. Capping is shown to exhibit significantly reduced exposure and risk relative to the dredging scenarios, even if potential undetected erosion of 5% of the cap is considered. Even with the improbable event of undetected failure of 25% of the cap, the exposure and risk associated with capping is approximately equal to or below all dredging scenarios. A preference for dredging due to the perception that it eliminates the long-term risk of in situ capping is not supported by this analysis. Although strictly applicable only to the Lower Fox River, the results suggest sitespecific analyses must be conducted to determine which sediment management approaches minimize the potential for long-term exposure and risk.     

A Caution for Monte Carlo Risk Assessment of Long Term Exposures based on Short-Term Exposure Study Data

Monte Carlo risk assessments commonly take as input empirical or parametric exposure distributions from specially designed exposure studies. The exposure studies typically have limited duration, since their design is based on statistical and practical factors (such as cost and respondent burden). For these reasons, the exposure period studied rarely corresponds to the biologic exposure period, which we define as the time at risk that is relevant for quantifying exposure that may result in health effects. Both the exposure period studied and the biologic exposure period will often differ from the exposure interval used in a Monte Carlo analysis. Such time period differences, which are often not accounted for, can have dramatic effects on the ultimate risk assessment. When exposure distributions are right skewed and/or follow a lognormal distribution, exposure will usually be overestimated for percentiles above the median by direct use of exposure study empirical data, since biologic exposure periods are generally longer than the exposure periods in exposure assessment studies. We illustrate the effect that biologic exposure time period and response error can have on exposure distributions, using soil ingestion as an example. Beginning with variance components from lognormally distributed soil ingestion estimates, we illustrate the effect of different modeling assumptions, and the sensitivity of the resulting analyses to these assumptions. We develop a strategy for determining appropriate exposure input distributions for soil ingestion, and illustrate this using data on soil ingestion in children.     

The effect of selenium and organic material in lake sediments on the bioaccumulation of methylmercury by Lumbriculus variegatus (oligochaeta)

The accumulation of methylmercury (MeHg) to an oligochaete worm Lumbriculus variegatus (Müller) was measured in two different lake sediments in the laboratory. ¹⁴C-labelled MeHg was added to sediments at the nominal concentration of 95 ng/g dw sediment. Groups of six oligochaete worms were exposed in glass beakers to 35 g of spiked sediment for 14 days. The two sediments had organic carbon concentrations of 3.4% and 9.9% and natural selenium concentrations of 1.45 and 0.28 mg/kg (dw), respectively. After two weeks exposure, both the accumulation rate of MeHg and the body residue in the worms were much lower in the sediment having a high organic carbon content. The effect of selenium concentration in the sediment on bioaccumulation of MeHg in Lumbriculus variegatus was measured in one sediment (organic carbon 3.4% and Se 1.45 mg/kg) by adding sodiumselenite (Na₂SeO₃) at different concentrations. The added amounts of selenium were 0, 0.1, 0.5, 2.5, 15.0, and 50.0 mg Se/kg dry sediment. In this exposure the nominal concentration of MeHg was 102 ng/g dw sediment. The two lowest selenium concentrations did not affect the bioaccumulation of MeHg. But, the dose of 2.5 mg Se/kg resulted in a 25% reduction in the body residue after two weeks exposure. When 15 and 50 mg Se/kg were added to the sediment the accumulation of MeHg in the organisms was decreased by 75% and 86%, respectively, as compared to the reference.     

工业毒物危险度估测的概率模型

本文提出一个危险度估测的对数正态概率模型,用此模型可建立某已知各浓度反应概率资料的反应经典曲线,估测不同浓度下总体的反应概率或个体被侵害的概率、某样本浓度的反应概率及某样本反应概率时的容许平均浓度.     

Quantitative Consideration of Ecosystem Characteristics in an Ecological Risk Assessment: A Case Study

Development of assessment endpoints and conceptual models aids ecological risk assessors in identifying measurable attributes that will allow quantification and prediction of risk. Measures of exposure and effect are explicitly considered, usually quantitatively, in nearly every ecological risk assessment, while measures of ecosystem characteristics are generally addressed only implicitly, if at all. Yet these characteristics influence both the behavior and location of assessment endpoint entities and the spatial and temporal distribution of stressors. This case study illustrates use of a regression partitioning model to quantify the influence of ecosystem characteristics (e.g., land use patterns, nutrient concentrations) on the concentration of a chemical stressor (atrazine) in surface waters of a large river basin. The model partitioned the basin into five land use groups ranging from High Forested to Very High Agriculture. Literature-derived chronic effects data were used with a joint-probability model to characterize atrazine risk to an aquatic assessment entity in each of these land use subgroups. Atrazine concentrations and risk directly correlated with the intensity of agricultural land use. This permits risk management to focus on agricultural areas within the basin; a focus that would not have been possible without explicitly considering ecosystem characteristics.