Residues of tetracyclines reach soils as a result of animal waste application. Sorption is a key process in transport, fate, and effects of contaminants in the environment. In this work, we have attempted to predict the sorption of four widely used tetracyclines (oxytetracycline, tetracycline, chlortetracycline, and doxycycline) from soil physicochemical properties. Batch sorption experiments were performed on 15 natural soils with a broad range of physicochemical properties, and the data were fitted to several isotherm models. Multivariate analysis methods were conducted to identify the main factors affecting the sorption distribution coefficients (K d) of the tetracyclines at two aqueous concentration levels (100 and 400 μg L−1). All four tetracycline sorption isotherms in alkaline and acidic soils were well described by the Freundlich and Langmuir equation, respectively. At intermediate soil pH (from 5.3 to 7), oxytetracycline and tetracycline exhibited Freundlich behavior, whereas chlortetracycline and doxycycline followed a Langmuir model. Two partial least squares (PLS) models were developed. The first one uses five soil descriptors as input variables; the second uses, pH, cation exchange capacity (CEC), and log K d,OTC. Both models satisfactorily predicted distribution coefficients within a factor of 1.5. Sorption of tetracyclines in soil is governed by several factors, in the following order of importance: solution speciation, CEC (dominant at acidic–neutral soil pH), transition metal content, and texture. The PLS models indicated that tetracycline sorption can be predicted using a minimal set of soil descriptors including oxytetracycline sorption data.

BACKGROUND: A climate-controlled pot experiment was conducted to investigate the effects of planting alfalfa and applying organic fertilizer on the dissipation of benzo[a]pyrene from an aged contaminated agricultural soil. RESULTS: Short-term planting of alfalfa inhibited the dissipation of benzo[a]pyrene from the soil by 8.9%, and organic fertilizer enhanced benzo[a]pyrene removal from the soil by 11.6% compared with the unplanted and unfertilized treatments, respectively. No significant interaction was observed between alfalfa and organic fertilizer on benzo[a]pyrene dissipation. Sterilization completely inhibited the removal of benzo[a]pyrene from the soil indicating that its degradation by indigenous microorganisms may have been the main mechanism of dissipation. Furthermore, significant positive relationships were observed between benzo[a]pyrene removal and the contents of soil ammonium nitrogen, nitrate nitrogen, and total mineral nitrogen at the end of the experiment, suggesting that competition between plants and microorganisms for nitrogen may have inhibited benzo[a]pyrene dissipation in the rhizosphere of alfalfa and the addition of organic fertilizer may facilitate microbial degradation of benzo[a]pyrene in the soil.

Threshold concentrations for treatment related effects of 31 insecticides, as derived from aquatic micro-/mesocosm tests, were used to calibrate the predictive value of the European Tier-1 acute effect assessment on basis of laboratory toxicity tests with Daphnia magna, Chironomus spp., Americamysis bahia and Gammarus pulex. The acute Tier-1 effect assessment on basis of Daphnia (EC50/100) overall was protective for organophosphates, carbamates and most pyrethroids but not for neonicotinoids and the majority of insect growth regulators (IGRs) in the database. By including the 28-day water-spiked Chironomus riparius test, the effect assessment improves but selecting the lowest value on basis of the 48-h Daphnia test (EC50/100) and the 28-day Chironomus test (NOEC/10) is not fully protective for 4 out of 23 insecticide cases. An assessment on basis of G. pulex (EC50/100) is sufficiently protective for 15 out of 19 insecticide cases. The Tier-1 procedure on basis of acute toxicity data (EC50/100) for the combination of Daphnia and A. bahia and/or Chironomus (new EU dossier requirements currently under discussion) overall is protective to pulsed insecticide exposures in micro-/mesocosms. For IGRs that affect moulting, the effect assessment on basis of the 48-h Chironomus test (EC50/100) may not always be protective enough to replace that of the water-spiked 28-day C. riparius test (NOEC/10) because of latency of effects.

INTRODUCTION: In Egypt, the picture of threats to humans and the environment from the exposure to organic pollutants is still incomplete. Thus the objectives of this study were to assess the occurrence and distribution of polychlorinated biphenyls (PCBs), organochlorine pesticides, and chlorpyrifos in sediments and mussels of Abu Qir Bay and their risks for environment and human health. MATERIALS AND METHODS: Twenty-three different compounds organochlorines were determined in 20 surfacial sediment and 10 mussel samples by gas chromatography-electron capture detector. A Screening Level Ecological Risk Assessment (SLERA) and a Human Health Risk Assessment (HHRA) were performed with the data. RESULTS AND DISCUSSION: ΣDDT (DDT, DDE, DDD) (average concentration 27 µg/kg dw) dominated the detected organic pollutants in the sediments, followed by CHLs (chlordane, heptachlor, heptachloro epoxide), hexachlorocyclohexane, chlorpyrifos, endosulfane, dieldrine, Σ6 PCBs, aldrine, hexachlorobenzene, pentachlorobenzene, methoxychlor, and mirex. In general, concentrations of Σ6 PCBs in mussels were higher than their corresponding sediment concentrations reflecting their relatively high bioavailability and bioaccumulative potential. However, concentrations of the organochlorine pesticides in mussels were lower than their corresponding sediment samples. Nevertheless, the SLERA on the bay sediments revealed that adverse ecological effects to benthic species are expected to occur whereas the HHRA showed that adverse health effects are not expected to occur from the consumption of the mussels. CONCLUSIONS: With the help of a SLERA, it was possible to indicate which class of chlorinated organic compounds is of highest concern to assess and to improve the environmental quality of the bay. Monitoring of organochlorines and chlorpyrifos would be needed to control the future trend of pollution.

PURPOSE: Urban waterways are impacted by diffuse stormwater runoff, yet other discharges can unintentionally contaminate them. The Okeover stream in Christchurch, New Zealand, receives air-conditioning discharge, while its ephemeral reach relies on untreated stormwater flow. Despite rehabilitation efforts, the ecosystem is still highly disturbed. It was assumed that stormwater was the sole contamination source to the stream although water quality data were sparse. We therefore investigated its water and sediment quality and compared the data with appropriate ecotoxicological thresholds from all water sources. METHODS: Concentrations of metals (Zn, Cu and Pb) in stream baseflow, stormwater runoff, air-conditioning discharge and stream-bed sediments were quantified along with flow regimes to ascertain annual contaminant loads. Metals were analysed by ICP-MS following accredited techniques. RESULTS: Zn, Cu and Pb concentrations from stormflow exceeded relevant guidelines for the protection of 90% of aquatic species by 18-, 9- and 5-fold, respectively, suggesting substantial ecotoxicity potential. Sporadic copper (Cu) inputs from roof runoff exceeded these levels up to 3,200-fold at >4,000 μg L−1 while Cu in baseflow from air-conditioning inputs exceeded them 5.4-fold. There was an 11-fold greater annual Cu load to the stream from air-conditioning discharge compared to stormwater runoff. Most Zn and Cu were dissolved species possibly enhancing metal bioavailability. Elevated metal concentrations were also found throughout the stream sediments. CONCLUSIONS: Environmental investigations revealed unsuspected contamination from air-conditioning discharge that contributed greater Cu annual loads to an urban stream compared to stormwater inputs. This discovery helped reassess treatment strategies for regaining ecological integrity in the ecosystem.

INTRODUCTION: This study presents bihourly, seasonal, and yearly concentration changes in volatile organic compounds (VOCs) in the inlet and effluent water of the wastewater treatment plant (WWTP) of a high-technology science park (HTIP) in Taiwan, with the VOC amounts at different sites correlated geologically. MATERIALS AND METHODS: This research adopted a combination of two systems, solid-phase microextraction with a gas chromatography/flame ionization detector and an assembly of purge and trap coupled with gas chromatography/mass spectrometry, to monitor polar and nonpolar VOCs in wastewater. This paper investigated the total VOCs, acetone, isopropyl alcohol (IPA), and dimethylsulfide (DMS) concentrations in real water samples collected in the ambient area of the HTIP. RESULTS AND DISCUSSION: The major contents of VOCs measured in the effluent of the WWTP in the HTIP and the surrounding river region were DMS (14–176 ppb), acetone (5–95 ppb), and IPA (15–316 ppb). In comparison with the total VOCs in the inlet wastewater of the WWTP, no corresponding relationship for total VOC concentration in the wastewater was observed between the inlet water and effluent water of the WWTP. CONCLUSIONS: The peak VOC concentrations appeared in the third season, and the correlation of different VOC amounts reflects the production situation of the factories. In addition, VOC concentrations at different sites indicate that the Ke-Ya River is seemingly an effective channel for transporting wastewater to its final destination. The data are good indications for the management of environmental pollution near the HTIP.

Many pharmaceuticals and related metabolites are not efficiently removed in sewage treatment plants and enter into surface water. There, they might be subject of drinking water abstraction and treatment by ozonation. In this study, a systematic approach for producing and effect-based testing of transformation products (TPs) during the drinking water ozonation process is proposed. For this, two pharmaceutical parent substances, three metabolites and one environmental degradation product were investigated with respect to their biodegradability and fate during drinking water ozonation. The Ames test (TA98, TA100) was used for the identification of mutagenic activity present in the solutions after testing inherent biodegradability and/or after ozonation of the samples. Suspicious results were complemented with the umu test. Due to the low substrate concentration required for ozonation, all ozonated samples were concentrated via solid phase extraction (SPE) before performing the Ames test. With the exception of piracetam, all substances were only incompletely biodegradable, suggesting the formation of stable TPs. Metformin, piracetam and guanylurea could not be removed completely by the ozonation process. We received some evidence that technical TPs are formed by ozonation of metformin and piracetam, whereas all tested metabolites were not detectable by analytical means after ozonation. In the case of guanylurea, one ozonation TP was identified by LC/MS. None of the experiments showed an increase of mutagenic effects in the Ames test. However, the SPE concentration procedure might lead to false-positive results due to the generation of mutagenic artefacts or might lead to false-negative results by missing adequate recovery efficiency. Thus, these investigations should always be accompanied by process blank controls that are carried out along the whole ozonation and SPE procedure. The study presented here is a first attempt to investigate the significance of transformation products by a systematic approach. However, the adequacy and sensitivity of the methodology need to be further investigated. The approach of combining biodegradation and ozonation with effect-based assays is a promising tool for the early detection of potential hazards from TPs as drinking water contaminants. It can support the strategy for the evaluation of substances and metabolites in drinking water. A multitude of possible factors which influence the results have to be carefully considered, among them the selectivity and sensibility of the mutagenicity test applied, the extraction method for concentrating the relevant compounds and the biocompatibility of the solvent. Therefore, the results have to be carefully interpreted, and possible false-negative and false-positive results should be considered.

This study investigated the effects of pH (6–10) and ozone dose [0.4–3.0 mg O3/mg dissolved organic carbon (DOC)] on the content and structure of haloacetic acid (HAA) precursors in groundwater rich in natural organic matter (NOM; DOC 9.85 ± 0.18 mg/L) during drinking water treatment. The raw water was ozonated in a 2 L glass column. NOM fractionation was carried out using XAD resins. HAA formation potential (HAAFP) was determined according to standard EPA Method 552. NOM characterization revealed it is mostly hydrophobic (65 % fulvic and 14 % humic acids). Hydrophobic NOM significantly influences HAA formation, as confirmed by the high HAAFP (309 ± 15 μg/L). Ozonation at pH 6–10 led to changes in NOM structure, i.e. complete humic acid oxidation, and increased the hydrophilic NOM fraction content (65–90 % achieved using 3.0 mg O3/mg DOC). The highest degree of NOM oxidation and HAA precursor removal was achieved at pH 10 (up to 68 % HAAFP). Ozonation pH influenced the distribution of HAA precursor content, as increasing the pH from 6 to 10 increased the reactivity of the hydrophilic fraction, with the HAAFP increasing from 19.1 ± 6.0 μg/mg DOC in raw water to 152 ± 8 μg/mg DOC in ozonated water. The degree of HAA precursor removal depends on the dominant oxidation mechanism, which is related to the applied ozone dose and the pH of the oxidation process. Ozonation at pH 10 favours the mechanism of radical NOM oxidation and was the most effective for HAAFP reduction, with the efficacy of the process improving with increasing ozone dose.

BDE-47 is one of the most widely found congeners of PBDEs in marine environments. The potential immunomodulatory effects of BDE-47 on fish complement system were studied using the marine medaka Oryzias melastigma as a model fish. Three-month-old O. melastigma were subjected to short-term (5 days) and long-term (21 days) exposure to two concentrations of BDE-47 (low dose at 290 ± 172 ng/day; high dose at 580 ± 344 ng/day) via dietary uptake of BDE-47 encapsulated in Artemia nauplii. Body burdens of BDE-47 and other metabolic products were analyzed in the exposed and control fish. Only a small amount of debrominated product, BDE-28, was detected, while other metabolic products were all under detection limit. Transcriptional expression of six major complement system genes involved in complement activation: C1r/s (classical pathway), MBL-2 (lectin pathway), CFP (alternative pathway), F2 (coagulation pathway), C3 (the central component of complement system), and C9 (cell lysis) were quantified in the liver of marine medaka. Endogenous expression of all six complement system genes was found to be higher in males than in females (p < 0.05). Upon dietary exposure of marine medaka to BDE-47, expression of all six complement genes were downregulated in males at day 5 (or longer), whereas in females, MBl-2, CFP, and F2 mRNAs expression were upregulated, but C3 and C9 remained stable with exposure time and dose. A significant negative relationship was found between BDE-47 body burden and mRNA expression of C1r/s, CFP, and C3 in male fish (r = −0.8576 to −0.9447). The above findings on changes in complement gene expression patterns indicate the complement system may be compromised in male O. melastigma upon dietary exposure to BDE-47. Distinct gender difference in expression of six major complement system genes was evident in marine medaka under resting condition and dietary BDE-47 challenge. The immunomodulatory effects of BDE-47 on transcriptional expression of these complement components in marine medaka were likely induced by the parent compound instead of biotransformed products. Our results clearly demonstrate that future direction for fish immunotoxicology and risk assessment of immunosuppressive chemicals must include parallel evaluation for both genders.

Phosphorus concentration in rivers results from both external inputs and internal loading from the bottom sediments. Seasonal, spatial, and multi-annual dynamics of phosphorus forms in bottom sediments and their interstitial water for the river Prut (Moldova) were evaluated. In order to determine content of total phosphorus in the bottom sediments, fresh (wet) samples were subjected to persulfate oxidation. The content of inorganic phosphorus was determined after acidic oxidation of samples. The amount of organic phosphorus was obtained by subtracting inorganic phosphorus from the amount of total phosphorus. Content of phosphorus forms in interstitial water was determined after centrifugation of fresh (wet) sediments. In general, the shape of dynamics of the amounts of inorganic phosphorus in sediments was close during years 2009, 2010, and 2011, with registered higher contents of this form on the middle course of the river. The spatial dynamics of organic phosphorus is less homogeneous along the Prut River. During 2009, higher amounts of organic phosphorus were recorded on the middle sector. During the spring of year 2010, the content of organic phosphorus in sediments was practically not changed along the river. The ratio of inorganic/organic phosphorus in bottom sediments was similar during the researched years, with the predominance of the inorganic phosphorus being recorded. Also, the increasing tendency of the percentage of organic phosphorus from spring to summer was identified. Generally, appropriate spatial and seasonal dynamics of phosphorus forms in bottom sediments and their interstitial water were recorded, although sometimes with some differences.