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.     

Accuracy assessment of a small-area method for estimating the spatial distribution of the degree of tree damage

Tree damage, gauged by the amount of defoliation, is one of the basic criteria used to determine treatments for protected and economic forests. Monitoring should include an assessment of the degree of tree damage in different spatial scales. Therefore, in addition to the commonly applied large-area methods, small-area methods should be used. The aim of the paper is to present the results of the accuracy assessment of a small-area method, proposed by Podlaski (2005) [Podlaski, R. (2005). Inventory of the degree of tree defoliation in small areas. Forest Ecology and Management, 215, 361–377], for monitoring the degree of tree damage. The degree of tree damage was shown in sub-blocks P₃ of the system of information on natural environment (SINUS). To estimate the spatial distribution of the degree of tree defoliation, survey sampling, based on simple random sampling with replacement (SRSWR), was used. The degree of damage to fir (Abies alba Mill.) and beech (Fagus sylvatica L.) was analysed in the Święty Krzyż forest section in the Świętokrzyski National Park. The maximum total estimation errors for the proportion of trees with a degree zero of damage, and with second and third degrees of damage together (for α = 0.05) were at most 30.8% for fir and 24.3% for beech trees. For standard, small-area evaluations, these are satisfactory values. In the Święty Krzyż forest section, the number of P₃ sub-blocks with 0.00–5.00% of undamaged trees and with 80.01–100.00% of moderately- or severely-damaged trees was significantly greater for fir than for beech. These results indicate that the fir population was unhealthier than the beech group in the study area. P₃ sub-blocks of the SINUS system, in which the proportion of the healthiest trees was highest, were situated at the forest margin, bordering on meadows and arable fields (in the case of fir) and forming dense patches consisting of several sub-blocks, or occurring singly in the whole study area (in the case of beech). The results show the significant differentiation of forest tree health in small areas.     

Kriging and Bilinear Methods for Estimating Spatial Pattern of Atmospheric Pollutants

Two statistical methods to reconstruct the spatial pattern ofenvironmental data are compared: the Kriging and the Bilinear.The comparison is performed by evaluating two differentcharacteristics of the methods: the interpolation and the estimation. The Kriging method is demonstrated to be better thanthe Bilinear regarding all the statistics studied, although thedifferences are not very significant. Especially, the Kriging ismore efficient than the Bilinear in the reconstruction of peakvalues and it does not extrapolate local trends. The methods areapplied to a set of environmental data measured in an urban area.     

Economics of place-based monitoring under the safe drinking water act, part I: spatial and temporal patterns of contaminants, and design of screening strategies

The goals of environmental legislation and associated regulations are to protect public health, natural resources, and ecosystems. In this context, monitoring programs should provide timely and relevant information so that the regulatory community can implement legislation in a cost-effective and efficient manner. The Safe Drinking Water Act (SDWA) of 1974 attempts to ensure that public water systems (PWSs) supply safe water to its consumers. As is the case with many other federal environmental statutes, SDWA monitoring has been implemented in relatively uniform fashion across the USA. In this three part series, spatial and temporal patterns in water quality data are utilized to develop, compare, and evaluate the economic performance of alternative place-based monitoring approaches to current monitoring practice. Under the Safe Drinking Water Act (SDWA), a common list of over 90 contaminants is analyzed nationwide using EPA-authorized laboratory procedures. National and state-level summaries of SDWA data have shown that not all contaminants occur in all places at all times. This hypothesis is confirmed and extended by showing that only a few (less than seven) contaminants are of concern in any one of 19 Iowa surface water systems studied. These systems collectively serve about 350,000 people and their sizes vary between 1,200 and 120,000. The distributions of contaminants found in these systems are positively skewed, with many non-detect measurements. A screening strategy to identify such contaminants in individual systems is presented. These findings have significant implications not only for the design of alternative monitoring programs, but also in multi-billion-dollar decisions that influence the course of future drinking water infrastructure, repair, and maintenance investments.     

Variation in spatial pattern of criteria air pollutants before and during initial rain of monsoon

Spatial patterns of various criteria air pollutants,like SO₂, NO₂, O₃, and TSP were studied atShahdara National Ambient Air Quality Monitoring stationin Delhi (India) in July 1999. The minimum pollutantconcentrations were observed during morning hours,whereas the highest concentrations were found during thelate night hours, which seem to be related with thevehicular emission. Pre-monsoon daily ambient airquality spatial pattern was compared with the spatialpattern during initial and subsequent rain shower ofmonsoon. These spatial patterns were found to beessentially the same before and during rain, however asignificant decrease in SO₂, NO₂ and TSPconcentrations (40-45%) was observed after initial andsubsequent rains of the monsoon, demonstrating theimportance of rainfall in the scavenging of thesecriteria air pollutants.     

Chemical techniques for assessing bioavailability of sediment-associated contaminants: SPME versus Tenax extraction

The traditional approach for predicting the risk of hydrophobic organic contaminants (HOCs) in sediment is to relate organic carbon normalized sediment concentrations to body residues or toxic effects to organisms. However, due to the multiple variables controlling bioavailability, this method has limitations. A matrix independent method of predicting bioavailability needs to be used in order to be universally applicable. Both chemical activity (freely dissolved chemical concentrations) measured by solid-phase microextraction (SPME) and bioaccessibility (rapidly desorbing fraction) estimated by Tenax extraction have been developed to predict bioavailability of sediment-associated HOCs. The objectives of this review are to summarize a number of studies using matrix-SPME or Tenax extraction to estimate bioavailability and/or toxicity of different classes of HOCs and evaluate the strengths and weakness of these two techniques. Although the two chemical techniques assess different components of the matrix, estimates obtained from both techniques have been correlated to organism body residues. The advantages of SPME fibers are their applicability for use in situ and their potential usage for a wide array of contaminants by selection of appropriate coatings. Single time-point Tenax extraction, however, is more time- and labor-effective. Tenax extraction also has lower detection limits, making it more applicable for highly toxic contaminants. This review also calls for additional research to evaluate the role of sequestrated contaminants and ingestion of sediment particles by organisms on HOC bioavailability. The use of performance reference compounds to reduce SPME sampling time and linking chemical based bioavailability estimates to toxicological endpoints are essential to expand the applications of these methods.     

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.     

Comparison of Groundwater Level Estimation Using Neuro-fuzzy and Ordinary Kriging

Water level in aquifer plays the main role in groundwater modeling as one of the input data. In practice, due to aspects of time and cost, data monitoring of water levels is conducted at a limited number of sites, and interpolation technique such as kriging is widely used for estimation of this variable in unsampled sites. In this study, the efficiency of the ordinary kriging (OK) and adaptive network-based fuzzy inference system (ANFIS) was investigated in interpolation of groundwater level in an unconfined aquifer in the north of Iran. The results showed that ANFIS model is more efficient in estimating the groundwater level than OK.     

Nutrient spatial pattern of the upstream,mainstream and tributaries of the Three Gorges Reservoir in China

A comprehensive monitoring program was conducted to investigate the nutrient spatial pattern in the mainstream of the Yangtze River from the Baihetan Dam down to the Three Gorges Dam located at the upper region of the Yangtze River in China. Samples were taken from 33 different sites from July 30 to August 19, 2011. The nutrient patterns of the three representative tributaries of the Three Gorges Reservoir (TGR)—the Modao, the Daning, and the Xiangxi Rivers—were also investigated. The results show that the mainstream of the TGR has a higher concentration of nitrogen and a lower concentration of phosphorus than that of the upper mainstream before the TGR. Moreover, it was found that nitrate-nitrogen (NO₃-N) is the main nitrogen component, while particulate phosphorus predominates the total phosphorus (TP). It was found that the three representative tributaries of the TGR have lower total nitrogen (TN) concentrations compared to the corresponding sections of the mainstream TGR. Based on the nutrient spatial pattern, the nutrient flux was calculated. The total fluxes of TN, NO₃-N, TP, and orthophosphate (PO₄-P) from the upstream reach into the TGR are 2,155.06, 1,674.97, 212.98, and 83.42 t day^?1, respectively. The amount of nutrients imported from the TGR into its tributaries is more than the amount exported. It was determined that the Xiangxi River has the largest net rate of imported nitrogen at 7.66 t day^?1, whereas the Daning River has the largest net rate of imported phosphorus at 1.75 t day^?1. In addition, compared with the nutrients imported from the TGR into its tributaries, the nutrient flux from the upstream reach into the TGR contributes approximately less than 3 %.     

The accumulation and effects of environmental contaminants on snakes: a review

In any ecological risk assessment, afull complement of the relevant members of theecosystems being studied should be considered. Reptiles in general, and snakes in particular, areimportant although often neglected components ofterrestrial and aquatic ecosystems and should beincluded in any study on environmental contamination. By neglecting reptiles, the risks posed by aparticular contaminant cannot be fully assessed. Since all snakes are secondary, tertiary, and toppredators, they are susceptible to the bioaccumulationof environmental contaminants. Their unique lifehistories make their roles in food webs diverse andimportant, and they are crucial to the properfunctioning of many ecological processes. We reviewand summarize organic and inorganic contaminant andradionuclide/radiation residue and lethal andsublethal effects data for snakes to stress theimportance of snakes and encourage their inclusion inecological risk assessments, to demonstrate thepaucity of available contaminant data on snakes andreveal the main information gaps, to encourage furtherecotoxicological studies on snakes, and to facilitatethe use of existing snake contaminant data inecological risk assessments. This review is the mostcomprehensive review currently available on theeffects on and accumulation of environmentalcontaminants in snakes.     

A method to combine non-probability sample data with probability sample data in estimating spatial means of environmental variables

In estimating spatial means of environmental variables of a region from datacollected by convenience or purposive sampling, validity of the results canbe ensured by collecting additional data through probability sampling. Theprecision of the estimator that uses the probability sample can beincreased by interpolating the values at the nonprobability sample points tothe probability sample points, and using these interpolated values as anauxiliary variable in the difference or regression estimator. Theseestimators are (approximately) unbiased, even when the nonprobability sampleis severely biased such as in preferential samples. The gain in precisioncompared to the estimator in combination with Simple Random Samplingis controlled by the correlation between the target variable andinterpolated variable. This correlation is determined by the size (density)and spatial coverage of the nonprobability sample, and the spatialcontinuity of the target variable. In a case study the average ratio of thevariances of the simple regression estimator and estimator was 0.68for preferential samples of size 150 with moderate spatial clustering, and0.80 for preferential samples of similar size with strong spatialclustering. In the latter case the simple regression estimator wassubstantially more precise than the simple difference estimator.     

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.     

Performance of semipermeable membrane devices for sampling of organic contaminants in groundwater

Lipid-filled semipermeable membrane devices (SPMDs) are receiving increasing attention as passive, in situ samplers for the assessment of environmental pollutant exposure. Although SPMDs have been successfully used in a variety of field studies in surface waters, only a few studies have addressed their characteristics as groundwater samplers. In this study, the performance of the SPMDs for monitoring organic contaminants in groundwater was evaluated in a pilot field application in an area severely contaminated by chemical waste, especially by chlorinated hydrocarbons. The spatial distribution of hydrophobic groundwater contaminants was assessed using a combination of passive sampling with SPMDs and non-target semiquantitative GC-MS analysis. More than 100 contaminants were identified and semiquantitatively determined in SPMD samples. Along the 6 field sites under investigation, a large concentration gradient was observed, which confirms a very limited mobility of hydrophobic substances in dissolved form in the aquifer. The in situ extraction potential of the SPMD is limited by groundwater flow, when the exchange volume of well water during an exposure is lower than the SPMD clearance volume for the analytes. This study demonstrates that SPMDs present a useful tool for sampling and analyzing of groundwater polluted with complex mixtures of hydrophobic chemicals and provides guidance for further development of passive sampling technology for groundwater.     

A risk-based screening approach for prioritizing contaminants and exposure pathways at Superfund sites

Contamination at Superfund sites can involve mixtures of chemicals and radionuclides in a variety of environmental media. Determining priorities for evaluation and remediation of various contaminants is an important part of the initial phases of any site investigation. An effective screening analysis at the beginning of the project can help by identifying both those situations in need of immediate remedial attention and those which require further sampling and evaluation. The screening approach discussed here is made up of two sets of calculations designed to provide upper- and lower-bound estimates of health risk to individuals likely to receive the highest exposures. This approach allows rapid identification of contaminants which pose a negligible risk and can be assigned a low priority for remedial attention or which pose a substantial risk and should be given the highest priority for appropriate remediation efforts. Contaminants designated as neither high- nor low-priority should be investigated in more detail prior to making decisions regarding the need for or method of remediation. The utility of this approach has already been demonstrated in the evaluation of contamination in the Clinch and Tennessee River systems originating from historical operations of atomic weapons and energy research facilities near Oak Ridge, Tennessee.     

Modeling the spatial pattern of farmland using GIS and multiple logistic regression: a case study of Maotiao River Basin, Guizhou Province, China

Land use change is an important topic in the field of global environmental change and sustainable development. Land use change modeling has attracted substantial attention because it helps researchers understand the mechanisms of land use change and assists regulatory bodies in formulating relevant policies. Maotiao River Basin is located in the province of Guizhou, China, which has a developed agricultural industry in the karst mountain areas. This paper selected biophysical and social–economic factors as independent variables, and constructed a multiple logistic regression of farmland spatial distribution probability by random sampling. Then, by using GIS technology and integrating the 2000 data, this study predicted the farmland spatial pattern. When the predicted map was compared with the actual farmland map for 2000, we noted that 71% of the simulation is in accordance with the 2000 farmland pattern. The result satisfactorily proves the reasonability and applicability of our model.     

A statistical F test for the natural attenuation of contaminants in groundwater

Natural attenuation (NA) is a catchall explanation for the overall decay and slowed movement of the contaminants in the subsurface. One direct support to NA is to demonstrate that contaminant concentrations from monitoring wells located near the source are decreasing over time. The decrease is summarily expressed in terms of an apparent half-life that is determinedfrom the line best fitting the observed log-transformed concentration data and time. This simple (time-only) decay modelassumes other factors are invariant, and so is flawed when complicating factors – such as a fluctuating water table – are present. A history of the water-table fluctuation can track changes in important NA factors like recharge, groundwater flow direction and velocity, as well as other non-NA factors like volume of water in and purged from the well before a sample is collected. When the trend in the concentrations is better associated with the water table rising or falling, any conclusionabout degradation rate may be premature. We develop simple regressions to predict contaminant concentration (c) by two line models: one involving time (c c(t)), and another involving groundwater elevation (c c(z)). We develop a third model that includesboth factors (c c(t, z)). Using an F-test to compare the fits to the models, we determine which modelis statistically better in explaining the observed concentrations. We applied the test to sites where benzene degradation rates had previously been estimated. The F-testcan be used to determine the suitability of applying non-parametric statistics, like the Mann-Kendall, to the concentration data, because the result from the F-test canindicate instability of the contaminant plume that may bemasked when the water table fluctuates.     

Community duplicate diet methodology: a new tool for estimating dietary exposures to pesticides

An observational field study was conducted to assess the feasibility of a community duplicate diet collection method; a dietary monitoring tool that is population-based. The purpose was to establish an alternative procedure to duplicate diet sampling that would be more efficient for a large, defined population, e.g., in the National Children's Study (NCS). Questionnaire data and food samples were collected in a residence so as not to lose the important component of storage, preparation, and handling in a contaminated microenvironment. The participants included nine Hispanic women of child bearing age living in Apopka, FL, USA. Foods highly consumed by Hispanic women were identified based on national food frequency questionnaires and prioritized by permethrin residue concentrations as measured for the Pesticide Data Program. Participants filled out questionnaires to determine if highly consumed foods were commonly eaten by them and to assess the collection protocol for the food samples. Measureable levels of permethrin were found in 54% of the samples. Questionnaire responses indicated that the collection of the community duplicate diet was feasible for a defined population.     

A tool for rapid screening of direct DNA agents using reaction rates and relative interaction potency: towards screening environmental contaminants for hazard

DNA damage represents a potential biomarker for determining the exposure risk to chemicals and may provide early warning data for identifying chemical hazards to human health. Here, we have demonstrated a simple chromatography-based method that can be used to rapidly screen for the presence of chemical hazards as well as to determine parameters relevant to hazard assessment. In this proof-of-principle study, a simple in vitro system was used to determine the interaction of pollutants and probable carcinogens, phenyl glycidyl ether (PGE), tetrachlorohydroquinone (Cl(4)HQ), methylmethane sulfonate (MMS), styrene-7,8-oxide (SO), and benzo[a]pyrene-7,8-dihydrodiol-9,10-epoxide (BPDE), a metabolite of benzo[a]pyrene (B[a]P), with single- and double-stranded DNA probes. Differences in potency and reaction kinetics were studied for chemical and DNA type. A relative interaction potency equivalency (PEQ) of a chemical was determined by ratio of interaction potency of a chemical to BPDE as the reference chemical in the reaction with single- and double-stranded oligodeoxynucleotides. PEQs were found to be BPDE > PGE > SO > MMS > Cl(4)HQ for single-stranded oligodeoxynucleotides while they were found to be BPDE > PGE > Cl(4)HQ > MMS > SO for double-stranded oligodeoxynucleotides. Kinetics evaluation revealed that BPDE reacted with both DNA probes at a significantly faster rate, as compared to the remaining test chemicals. Equilibrium was reached within an hour for BPDE, but required a minimum of 48 h for the remaining chemicals. First-order rate constants were (1.61 ± 0.2) × 10(-3) s(-1) and (3.18 ± 0.4) × 10(-4) s(-1) for reaction of BPDE with double- and single-stranded DNA, respectively. The remaining chemicals possessed rate constants from 2 to 13 × 10(-6) s(-1) with a relative kinetic order for reaction with DNA of BPDE ? MMS > SO > PGE > Cl(4)HQ for ds-DNA and BPDE ? SO ≈ Cl(4)HQ ≈ MMS > PGE for ss-DNA. We further found that the reaction potency, defined by dose-response between chemical pollutants and DNA, depends on the form of DNA present for reaction. Noteworthy, we found that relative PEQ did not follow the same kinetic trends. However, our preliminary findings suggest that reaction kinetics, in combination with relative interaction potency, may be a significant parameter that can be used to evaluate the hazard level of environmental pollutants.     

Comparison of PoraPak Rxn RP and XAD-2 adsorbents for monitoring dissolved hydrophobic organic contaminants

Accurate determination of the levels of dissolved hydrophobic organic contaminants (HOCs) is an important step in estimating the dynamics of their inputs and losses in aqueous systems. This study explores an alternative method for efficiently sampling dissolved HOCs while mitigating a number of sampling artifacts associated with traditional methods. The adsorption characteristics of a new polymeric resin, PoraPak Rxn RP (PPR), were assessed using sorption isotherm experiments and fixed bed adsorption studies. The adsorption capacities and breakthrough times for four model contaminants (phenol, p-nitrophenol, naphthalene, and 2,4,6-tribromophenol) were proportional to the contaminant’s hydrophobicity. The ability of PPR to isolate dissolved polychlorinated biphenyls (PCBs) in real samples was compared with that of XAD-2, a well-known macroporous polymer that suffers from high background contamination. The results indicated that the PPR resin can be effectively used for monitoring HOCs, with low ∑PCB levels in blanks, decreasing solvent use, and reducing extraction times.