Detection of the antimicrobials triclocarban and triclosan in agricultural soils following land application of municipal biosolids

The occurrence of the antimicrobials triclocarban (TCC) and triclosan (TCS) was investigated in agricultural soils following land application of biosolids using liquid chromatography-tandem mass spectrometry (LC-MS-MS) with negative ion multimode ionization. The method detection limits were 0.58 ng TCC/g soil, 3.08 ng TCC/g biosolids, 0.05 ng TCS/g soil and 0.11 ng TCS/g biosolids and the average recovery from all of the sample matrices was >95%. Antimicrobial concentrations in biosolids from three Michigan wastewater treatment plants (WWTPs) ranged from 4890 to 9280 ng/g, and from 90 to 7060 ng/g, for TCC and TCS respectively. Antimicrobial analysis of soil samples, collected over two years, from ten agricultural sites previously amended with biosolids, indicated TCC was present at higher concentrations (1.24-7.01 ng/g and 1.20-65.10 ng/g in 2007 and 2008) compared to TCS (0.16-1.02 ng/g and from the method detection limit, <0.05-0.28 ng/g in 2007 and 2008). Soil antimicrobial concentrations could not be correlated to any soil characteristic, or to the time of last biosolids application, which occurred in either 2003, 2004 or 2007. To our knowledge, our data represent the first report of TCC, and the first comparison of TCC and TCS concentrations, in biosolids-amended agricultural soils. Such information is important because approximately 50% of US biosolids are land applied, therefore, any downstream effects of either antimicrobial are likely to be widespread.     

Evolution of antibiotic occurrence in a river through pristine, urban and agricultural landscapes

A river along the semi-arid Front Range of Colorado was monitored for antibiotics including five tetracycline and six sulfonamide compounds. Existing analytical methods were adapted to measure these compounds in a surface water matrix at environmentally relevant concentrations (0.05 microg/L). Natural organic matter present in surface waters was confirmed to significantly impact the low-level analysis of tetracyclines (TCs) necessitating the use of standard addition quantification techniques. Five sites along the Cache la Poudre River were monitored for antibiotics encompassing pristine areas without anthropogenic influence, urban areas impacted by wastewater discharges and agricultural areas susceptible to non-point source contaminant runoff. The only site at which no antibiotics were detected was the pristine site in the mountains before the river had encountered urban or agricultural landscapes. By the time the river had exited the urban area, 6 of the 11 antibiotic compounds that were monitored were found in the samples. At Site 5, which had both urban and agricultural influences all five of the TCs monitored were detected indicating both urban and agricultural influences. The concentration of TCs at Site 5 ranged from 0.08 to 0.30 microg/L.     

Association of manganese effluent with the application of fertilizer and manure on tea field

Manganese (Mn) concentrations in the tea field effluent were 1.1-3.5 mg/l over a 2 year period from June 1997 to May 1998 (first water year) and June 1998 to May 1999 (second water year). The annual Mn loads were 38,000 g/ha in the first water year and 19,000 g/ha in the second. The highest Mn loads were observed, respectively, in July 1997 (10,000 g/ha) in the first water year and in June 1998 (4100 g/ha) in the second. The water-soluble Mn content of soil of the tea field increased abruptly with decreasing soil pH in the pH region below 4.5. The large Mn load from the tea field during the rainy season is likely due to application of excess fertilizer and manure before the rainy season, which may lead to acidification of the soil.     

Cu, Cr and As distribution in soils adjacent to CCA-treated utility poles in Eastern Blacksea Region of Turkey

In this study, the main objective was to asses the distribution of Cu, Cr, and As in soils adjacent to CCA-treated utility poles in Eastern Blacksea Region of Turkey (Trabzon, Rize and Artvin ) and determine the influence of soil composition.

Surface (0–5 cm) and subsurface soil samples (30–40 cm) were collected near CCA-treated utility poles and control soil samples away from CCA-treated utility poles were also collected. Water holding capacity, pH and mechanical properties of soil samples were determined for both depth levels.

Results showed that Cu, Cr and As concentration in soil samples taken from all three cities in 0–5 cm depth was higher than soil samples taken from 30–40 cm depth. Cu, Cr and As concentrations were much higher in soil samples taken from city of Rize     

Investigation of extraction and clean-up procedures used in the quantification and stable isotopic characterisation of PAHs in contaminated urban soils

Four different extraction methods, soxhlet, soxtherm, sonication and accelerated solvent extraction (ASE), were used to isolate the 16 priority pollutant PAHs from a certified reference soil (LGC 6140) and from a contaminated soil (BG CLR 17). Based on SIM-GC-MS results, all methods were found to give accurate and highly reproducible concentration data. There was, however, significant between-method and sometimes within-method variability in the stable carbon isotope signatures obtained for individual PAHs from the contaminated soil (BG CLR 17) using GC-C-IRMS. When two clean-up procedures, silica/dichloromethane and alumina/hexane/toluene, were used to remove co-extracted material, however, it was found that ASE gave the more consistent and reproducible stable carbon isotope data. These findings are likely to be of importance for the characterisation of natural and anthropogenic organic matter and, in particular, in source identification and apportionment studies.     

Differentiation in the fertility of Inceptisols as related to land use in the upper Solimões river region, western Amazon

The Upper Solimões river region, western Amazon, is the homeland of indigenous populations and contains small-scale agricultural systems that are important for biodiversity conservation. Although traditional slash-and-burn agriculture is being practiced over many years, deforestation there is relatively small compared to other Amazon regions. Pastures are restricted to the vicinity of cities and do not spread to the small communities along the river. Inceptisols are the main soil order (>90%) in the area and have unique attributes including high Al content and high cation exchange capacity (CEC) due to the enrichment of the clay fraction with 2:1 secondary aluminosilicates. Despite its importance, few studies have focussed on this soil order when considering land use effects on the fertility of Amazon soils. Thus, the objective of this study was to evaluate changes in soil fertility of representative land use systems (LUSs) in the Upper Solimões region, namely: primary rainforest, old secondary forest, young secondary forest, agroforestry, pasture and agriculture. LUSs were significantly differentiated by the chemical attributes of their topsoil (0-20 cm). Secondary forests presented soil chemical attributes more similar to primary rainforest areas, while pastures exhibited the highest dissimilarity from all the other LUSs. As a whole, soil chemical changes among Inceptisols dominated LUSs showed patterns that were distinct from those reported from other Amazon soils like Oxisols and Ultisols. This is probably related to the presence of high-activity clays enriched in exchangeable aluminum that heavily influenced the soil chemical reactions over the expected importance of organic matter found in most studies conducted over Oxisol and Ultisol.     

Concentrations, sources, and spatial distribution of individual polycyclic aromatic hydrocarbons (PAHs) in agricultural soils in the Eastern part of the EU: Poland as a case study

Soils from agricultural areas receive unsatisfactory attention as regards the contamination with organic pollutants. To answer those needs the contents of the sixteen individual PAH compounds were determined (GC/MS technique) in agricultural soils in Poland. The samples (n = 216) were collected from the upper layer of arable land in the year 2005. Half of the samples represented typical rural areas, while the rest derived from the territories potentially subjected to the urban/industrial pressure of various intensity. The mean (geometric) content of individual compounds varied from 1 μg kg^− 1 for acenaphtylene to 55 μg kg^− 1 for fluoranthene with the highest contributions (11.6%-12.9%) of phenanthrene, fluoranthene and pyrene. Higher molecular weight PAHs (4 rings) were strongly linked mutually and with the ∑16PAHs. They contributed substantially (73%) to the overall content of PAHs, which implies domination of anthropogenic sources. The calculated molecular indexes suggest that most of those PAHs derive from the combustion of coal, the main energy source in Poland. Simultaneously, the concentrations of lower molecular weight compounds seem to reflect the background, “natural” PAH compounds, which represent mainly atmospherically distributed emission. The division of the samples into groups describing geographical regions and landscape type enabled evaluation of the spatial trends in contamination of soils with PAH compounds. The most pronounced effect of spatial parameters corresponded to PAHs > 4 rings, while lower molecular weight compounds showed more homogeneous concentration through the country.     

Modelling of the long-term fate of pesticide residues in agricultural soils and their surface exchange with the atmosphere: Part II. Projected long-term fate of pesticide residues

In the first part of this paper, a simple coupled dynamic soil-atmosphere model for studying the gaseous exchange of pesticide soil residues with the atmosphere is described and evaluated by comparing model results with published measurements of pesticide concentrations in air and soil. In Part II, the model is used to study the concentration profiles of pesticide residues in both undisturbed and annually tilled agricultural soils. Future trends are estimated for the measured air and soil concentrations of lindane and six highly persistent pesticides (toxaphene, p,p'-DDE, dieldrin, cis- and trans-chlordane and trans-nonachlor) over a twenty-year period due to volatilization and leaching into the deeper soil. Wet deposition and particle associated pesticide deposition (that increase soil residue concentrations) and soil erosion, degradation in the soil (other than for lindane) and run-off in precipitation are not considered in this study. Estimates of the rain deposition fluxes are reported that show that, other than for lindane, net volatilization fluxes greatly exceed rain deposition fluxes. The model shows that the persistent pesticides studied are highly immobile in soil and that loss of these highly persistent residues from the soil is by volatilization rather than leaching into the deeper soil. The soil residue levels of these six pesticides are currently sources of net volatilization to the atmosphere and will remain so for many years. The maximum rate of volatilization from the soil was simulated by setting the atmospheric background concentration to zero; these simulations show that the rates of volatilization will not be significantly increased since soil resistance rather than the atmospheric concentration controls the volatilization rates. Annual tilling of the soils increases the volatilization loss to the atmosphere. Nonetheless, the model predicts that, if only air-soil exchange is considered, more than 76% of current persistent pesticide residues will remain after 20 years in the top 7 cm of annually tilled soils. In contrast, lindane is relatively mobile in soil due to weaker binding to soil carbon and leaching of lindane into soil is the main removal route for current lindane residues near the soil surface. The model predicts that the soil is a sink for lindane in the atmosphere and that soil residue levels of lindane in the surface soil are determined by a balance between dry gaseous deposition to the soil from the atmosphere and leaching from the surface soil into the deeper soil where degradation is the dominant loss route. The model suggests that deposition of lindane from the atmosphere will sustain residues in the soil and, in the absence of fresh applications of lindane to the soil, eliminating lindane from the atmosphere would lead to a rapid decline of lindane residues in agricultural soils of the southern U.S.     

Multivariate analysis of the geochemistry and mineralogy of soils along two continental-scale transects in North America

Soils collected in 2004 along two North American continental-scale transects were subjected to geochemical and mineralogical analyses. In previous interpretations of these analyses, data were expressed in weight percent and parts per million, and thus were subject to the effect of the constant-sum phenomenon. In a new approach to the data, this effect was removed by using centered log-ratio transformations to ‘open’ the mineralogical and geochemical arrays. Multivariate analyses, including principal component and linear discriminant analyses, of the centered log-ratio data reveal the effects of soil-forming processes, including soil parent material, weathering, and soil age, at the continental-scale of the data arrays that were not readily apparent in the more conventionally presented data. Linear discriminant analysis of the data arrays indicates that the majority of the soil samples collected along the transects can be more successfully classified with Level 1 ecological regional-scale classification by the soil geochemistry than soil mineralogy. A primary objective of this study is to discover and describe, in a parsimonious way, geochemical processes that are both independent and inter-dependent and manifested through compositional data including estimates of the elements and corresponding mineralogy.     

Measuring the saturation limit of low-volatility organic compounds in soils: implications for estimates of dermal absorption

Estimating dermal absorption from contaminated soils typically requires extrapolations from measurements obtained on soils artificially contaminated at much larger concentrations. Such extrapolations should be constrained by the fact that maximum absorption will occur for the largest possible concentration of chemical on the soil without neat chemical being present; i.e., at the soil saturation limit (S_soil). Saturation limits of two low-volatility model compounds (4-cyanophenol and methyl paraben) were determined on the 38-63 μm sieve fraction of four soils with different fractions of organic carbon (f_oc = 0.015-0.45) and specific surface areas (σ_soil = 4-34 m² g^− 1) using two methods: equilibrium uptake into silicone rubber membranes and differential scanning calorimetry. Except for Pahokee peat, which had the largest f_oc, a model assuming contributions from both surface adsorption and organic carbon absorption provided excellent predictions of S_soil. In all soils, the surface saturation concentration of both chemicals was estimated at 2.2 mg m^− 2. The saturation concentration of 4-cyanophenol in the soil organic carbon was 1.7-fold higher than methyl paraben, which is consistent with the estimated solubility limits of these two chemicals in octanol.     

Early Hg mobility in cultivated tropical soils one year after slash-and-burn of the primary forest, in the Brazilian Amazon

In the Brazilian Amazon, forest conversion to agricultural lands (slash-and-burn cultivation) contributes to soil mercury (Hg) release and to aquatic ecosystem contamination. Recent studies have shown that soil Hg loss occurs rapidly after deforestation, suggesting that Hg mobility could be related to the massive cation input resulting from biomass burning. The objective of this research was to determine the effects of the first year of slash-and-burn agriculture on soil Hg levels at the regional scale of the Tapajós River, in the state of Pará, Brazilian Amazon. A total of 429 soil samples were collected in 26 farms of five riparian communities of the Tapajós basin. In September 2004, soil samples were collected from primary forest sites planned for slash-and-burn cultivation. In August 2005, one year after the initial burning, a second campaign was held and the exact same sites were re-sampled. Our results showed that total Hg levels in soils did not change significantly during the first year following slash-and-burn, suggesting no immediate release of soil Hg at that point in time. However, an early Hg mobility was detected near the surface (0-5 cm), reflected by a significant shift in Hg distribution in soil fractions. Indeed, a transfer of Hg from fine to coarser soil particles was observed, indicating that chemical bonds between Hg and fine particles could have been altered. A correspondence analysis (CA) showed that this process could be linked to a chemical competition caused by cation enrichment. The regional dimension of the study highlighted the prevailing importance of soil types in Hg dynamics, as shown by differentiated soil responses following deforestation according to soil texture. Confirming an early Hg mobility and indicating an eventual Hg release out of the soil, our results reinforce the call for the development of more sustainable agricultural practices in the Amazon.     

Grouted and concreted soils: residue mapping of foundation techniques in Flanders,Belgium

Sand is one of the main raw materials used in infrastructure and road construction. While it is a common natural raw material worldwide, the locations where it can be found are not evenly distributed. Because Flanders is highly dependent on imported sand, there is a need to find alternatives. One alternative might be found in the residues from foundation techniques like grout, soil mixed with bentonite, and cemented soils. This paper reports an attempt to determine the annual amount of residues from these foundation techniques available on the Flemish market, by use of a market study. This study estimated that the annual amount of grouted soils and cemented soil remainders is more than 40% of the annual amount of natural sands dredged from the Belgian Continental Shelf. Preliminary tests show that grout and cemented soil remainders could be a valuable replacement for natural sand currently used in low grade applications like sub foundations and stabilized sands.     

Total and extractable contents of trace metals in agricultural soils of the Valderas area, Spain

The surface horizons of four agricultural field soils (Mollic ustifluvents, Alfic Xerochrepts, Typic Palexeralfs, Typic Haploxeralfs) were sampled to determine the total copper, cobalt, molybdenum, zinc, chromium, nickel, selenium, cadmium, lead, mercury, lithium and strontium, and were also fractionated by an extraction procedure to estimate the quantities of these trace metals in soluble form. The extractants used were the following: 1.0 N NH4 OAc for lithium and strontium, 0.05 M Na2-EDTA for cadmium, copper, nickel and zinc, 2.5% (w/v) acetic acid for lead, 2.5% (w/v) acetic acid and 2% (w/v) dithizone for cobalt, 2% (w/v) diethyldithiocarbamate solution for selenium, 0.1 NHCl for chromium, and 0.5 NHCl for mercury. The total content of these twelve elements in the four field soils sampled were lower than the levels quoted in the literature, although for different geochemical systems. The percentage of the total element content in soluble form was (except for selenium) generally very low, averaging between 5.5 and 8% for copper, 1.6 and 2.5% for cobalt, 8 and 10% for molybdenum, 1.8 and 2.2% for zinc, 14.2 and 17.7% for chromium, 5.5 and 6.4% for nickel, 30 and 55% for selenium, 8 and 14% for cadmium, 3 and 3.6% for lead, 8.3 and 11% for mercury, 5 and 7% for lithium, and 4.4 and 5.7% for strontium, regardless of the soil type.     

Distributions of polycyclic aromatic hydrocarbons in surface waters, sediments and soils of Hangzhou City, China

Ten polycyclic aromatic hydrocarbons (PAHs) were simultaneously measured in 17 surface water samples and 11 sediments of four water bodies, and 3 soils near the water-body bank in Hangzhou, China in December 2002. It was observed that the sum of PAHs concentrations ranged from 0.989 to 9.663 microg/L in surface waters, from 132.7 to 7343 ng/g dry weight in sediments, and from 59.71 to 615.8 ng/g dry weight in soils. The composition pattern of PAHs by ring size in water, sediment and soil were surveyed. Three-ring PAHs were dominated in surface waters and soils, meanwhile sediments were mostly dominated by four-ring PAHs. Furthermore, PAHs apparent distribution coefficients (K(d)) and solid f(oc)-normalized K(d) (e.g. K(oc)= K(d) / f(oc)) were calculated. The relationship between logK(oc) and logK(ow) of PAHs for field data on sediments and predicted values were compared. The sources of PAHs in different water bodies were evaluated by comparison of K (oc) values in sediments of the river downstream with that in soils. Hangzhou section of the Great Canal was heavily polluted by PAHs released from industrial wastewater in the past and now PAHs in sediment may serve as sources of PAHs in surface water. PAHs in Qiantang River were contributed from soil runoff. Municipal road runoff was mostly contributed to West Lake PAHs.     

Concentrations, enantiomeric compositions, and sources of HCH, DDT and chlordane in soils from the Pearl River Delta, South China

Concentrations, and enantiomeric compositions of HCH, DDT and chlordane in 74 soils of the Pearl River Delta, South China were investigated. The mean concentrations of HCHs and DDTs descended in the order: crop soils>paddy soils>natural soils. The concentrations (ng/g dw) of p,p'-DDE, p,p'-DDT, p,p'-DDD and o,p'-DDT in crop soils were 0.14-231, 0.07-315, 0.5. An EF value >0.5 generally suggested a preferential degradation of the (-) enantiomers of both TC and CC. The racemic alpha-HCH observed in the soils with higher HCH concentrations indicated that the transformation from gamma-HCH (e.g. lindane) to alpha-HCH may be an important process in the soils. The isomer ratios of p,p'-DDT/(DDE+DDD), o,p'-DDT/p,p'-DDT and enantiomeric compositions of o,p'-DDT suggested that both illegal use of technical DDT and the DDT impurity in dicofol may be responsible for the freshly DDT input in the region. The sources of DDTs were drawn by principal component analysis-multiple linear regression (PCA-MLR). The relative contributions of dicofol-type DDT, residues, and fresh technical DDT were estimated to be 55%, 21% and 17%, respectively. In addition, CC was found to degraded faster than TC in soils from the Pearl River Delta. The study demonstrated that the combination of isomer ratios and enantiomeric composition analysis may provide critical information on the potential sources and fate of organochlorine pesticides in soil.     

Analysis of composition, distribution and origin of hexachlorocyclohexane residues in agricultural soils from NW Spain

Concentrations of the isomers of the organochlorine pesticide hexachlorocyclohexane (HCH) were determined in 252 surface soil samples collected within a sampling network covering agricultural areas in Galicia (NW Spain). The concentration of total HCH (sum of α + β + γ + δ) ranged between 4 and 2305 ng g⁻¹ (dry weight), with the α-HCH and γ-HCH isomers predominating (< 1-1404 ng g⁻¹ and < 1-569 ng g⁻¹, respectively). The distribution of the pesticide residues was very heterogeneous, with the largest concentrations present in one of the studied areas (the province of A Coruña). The distribution of HCH was not found to be related to any soil property (organic matter, pH, clays, and metals). Multivariate statistical analysis of the data revealed that three populations of samples with a defined composition of HCH, can be related to the source of HCH: technical HCH (α/γ > 3), lindane (99% γ-HCH), or both. The existence of a third population consisting almost exclusively of α-HCH suggests that background contamination of anthropogenic origin dates from several decades ago. The detailed analysis of these populations enabled the possible temporal scale of the application of these pesticides to be deduced.     

步行商业街环境和使用行为调查与多元统计分析 ——结合珠海莲花路步行街改造

该文利用问题式问卷和语义差别法对珠海市莲花路商业街现状进行了实态调查，并利用 计算机对调查数据作了平均值分析，相关分析，因子分析等多元统计分析，得到明确的以数据作表述的结论，作为步行商业街下一步规划的参考。     

A lead isotopic study of the human bioaccessibility of lead in urban soils from Glasgow, Scotland

The human bioaccessibility of lead (Pb) in Pb-contaminated soils from the Glasgow area was determined by the Unified Bioaccessibility Research Group of Europe (BARGE) Method (UBM), an in vitro physiologically based extraction scheme that mimics the chemical environment of the human gastrointestinal system and contains both stomach and intestine compartments. For 27 soils ranging in total Pb concentration from 126 to 2160 mg kg^− 1 (median 539 mg kg^− 1), bioaccessibility as determined by the ‘stomach’ simulation (pH ~ 1.5) was 46-1580 mg kg^− 1, equivalent to 23-77% (mean 52%) of soil total Pb concentration. The corresponding bioaccessibility data for the ‘stomach + intestine’ simulation (pH ~ 6.3) were 6-623 mg kg^− 1 and 2-42% (mean 22%) of soil Pb concentration. The soil ²⁰⁶Pb/²⁰⁷Pb ratios ranged from 1.057 to 1.175. Three-isotope plots of ²⁰⁸Pb/²⁰⁶Pb against ²⁰⁶Pb/²⁰⁷Pb demonstrated that ²⁰⁶Pb/²⁰⁷Pb ratios were intermediate between values for source end-member extremes of imported Australian Pb ore (1.04) - used in the manufacture of alkyl Pb compounds (1.06-1.10) formerly added to petrol - and indigenous Pb ores/coal (1.17-1.19). The ²⁰⁶Pb/²⁰⁷Pb ratios of the UBM ‘stomach’ extracts were similar (< 0.01 difference) to those of the soil for 26 of the 27 samples (r = 0.993, p < 0.001) and lower in 24 of them. A slight preference for lower ²⁰⁶Pb/²⁰⁷Pb ratio was discernible in the UBM. However, the source of Pb appeared to be less important in determining the extent of UBM-bioaccessible Pb than the overall soil total Pb concentration and the soil phases with which the Pb was associated. The significant phases identified in a subset of samples were carbonates, manganese oxides, iron-aluminium oxyhydroxides and clays.     

Effects of recreational activities on the soil and water components of a deciduous forest ecosystem in Turkey

Impacts of recreational activities on some hydrological properties of a deciduous forest ecosystem related to water production have been evaluated with an inclusive soil study, coupled with a two‐year water quality monitoring program. Spatial variations of water quality parameters did not indicate a statistically significant deterioration caused by the recreational activities in the stream water, but the effects of trampling on physical soil properties were clear. The bulk density of the soils increased with the intensity of recreation from 1.18 to 1.29 g cm^?3, while the percentage of clay fraction decreased, as an indicator of erosion. The soils of the stream banks in the recreation area had reasonable saturated hydraulic conductivity values, and were affected sharply by the intensity of recreational use. The low inclination (0.5%) and the coarse texture of the soils were possibly the main factors diminishing or concealing the trampling effects not observed on the water quality of the stream passing through the recreation area.     

Microzonation of the Plio-Quaternary soils: a study of the liquefaction risk potential in the Lake Van Basin,Turkey

Yüzüncü Yıl University (YYU) campus area is located on the eastern shore of Lake Van, within one of the active tectonic belts of Eastern Anatolia. The sediments accumulated in a lake formed when the Murat River was dammed by volcanoclastic deposits and hence include lacustrine, fluvial and sandy shore sediments. In order to delineate the liquefaction-prone soils, geological and geophysical data were assessed. On the basis of the Liquefaction Potential Index (I_L), three main geotechnical zones were identified in the study area and three microzones were delineated within the university campus to reflection the potential damage to structures.